Selective safened herbicidal composition

ABSTRACT

Mixtures of a herbicidally effective amount of a pyridylsulfonylurea of formula I,   &lt;IMAGE&gt; (I)  wherein R, R1, R2 and A are as defined in claim 1, and of a herbicide-antagonistically effective amount of a sulfamoylphenylurea of formula II,   &lt;IMAGE&gt; (II)  wherein R7 to R11 and A2 are as defined in claim 1, are very suitable for controlling weeds in crops of useful plants, especially maize and sugar cane.

This is a continuation of Ser. No. 291,319, filed Aug. 16, 1994,abandoned, which is a continuation of Ser. No. 157,870, filed Nov. 24,1993, abandoned.

The present invention relates to a selective herbicidal composition forcontrolling grasses and weeds in crops of useful plants, especially incrops of maize and sugar cane, which composition comprises a herbicideand a safener (counter-agent, antidote) which protects the usefulplants, but not the weeds, against the phytotoxic action of theherbicide, and to the use of that composition or the combination ofherbicide and safener in the control of weeds in crops of useful plants.

When using herbicides, the cultivated plants may suffer considerabledamage, depending on such factors as, for example, the amount ofherbicide and the method of application, the species of cultivatedplant, the nature of the soil and climatic conditions, such as, forexample, hours of daylight, temperature and amounts of rainfall. Severedamage may occur especially when, in the course of crop rotation,cultivated plants that are resistant to the herbicides are followed byother cultivated plants that have no, or only insufficient, resistanceto the herbicides.

In order to deal with that problem, several substances have already beenproposed that are capable of specifically antagonising the harmfuleffect of the herbicide on the cultivated plant, that is to say, arecapable of protecting the cultivated plant without having anyappreciable influence on the herbicidal action on the weeds to becontrolled. It has been found that the proposed safeners often exhibit avery species- or type-specific action both with respect to thecultivated plants and with respect to the herbicide, and in some casesalso in dependence on the method of application, that is to say, aspecific safener is often suitable only for a specific cultivated plantand a specific class of herbicidal substance.

For example, sulfamoylphenylureas known from EP-A-0 365 484 are suitablefor protecting cultivated plants against the phytotoxic action of a veryspecific class of pyridylsulfonylurea herbicides.

Accordingly, a selective herbicidal composition is proposed according tothe invention which comprises as active component, together with inertcarriers and adjuvants, a mixture of

a) a herbicidally effective amount of a pyridylsulfonylurea of formula I##STR3## wherein R is hydrogen, halogen, C₁ -C₄ alkyl, C₁ -C₄ alkoxy orC₁ -C₄ alkylthio, or is C₁ -C₄ alkyl mono- or poly-substituted byhalogen; R₁ is hydrogen or methyl; R₂ is methyl or methoxy; A is --X--R₃or --N--(R₄)R₅ ; R₃ is C₁ -C₆ alkyl, or C₁ -C₆ alkyl that is mono- orpoly-substituted by halogen, C₁ -C₆ alkoxy, C₃ -C₆ alkenyloxy, C₃ -C₆alkynyloxy or by C₃ -C₆ cycloalkyl, which may for its part beinterrupted by oxygen; or is C₃ -C₆ alkenyl, or C₃ -C₆ alkenyl that ismono- or poly-substituted by halogen, C₁ -C₆ alkoxy, C₃ -C₆ alkenyloxyor by C₃ -C₆ alkynyloxy; or is C₄ -C₆ cycloalkyl, or C₄ -C₆ cycloalkylthat is mono- or poly-substituted by halogen or by C₁ -C₆ alkoxy; or isC₃ -C₆ cycloalkyl that is interrupted by oxygen; or is C₃ -C₆ alkynyl; Xis oxygen or S(O)_(n) ; n is 0, 1 or 2; R₄ is hydrogen, C₁ -C₆ alkyl, orC₁ -C₆ alkyl that is mono- or poly-substituted by halogen, C₁ -C₆alkoxy, C₃ -C₆ alkenyloxy, C₃ -C₆ alkynyloxy or by C₁ -C₆ alkylthio; R₅is hydrogen, C₁ -C₆ alkyl, or C₁ -C₆ alkyl that is mono- orpoly-substituted by halogen, C₁ -C₆ alkoxy, C₃ -C₆ alkenyloxy, C₃ -C₆alkynyloxy or by C₁ -C₆ alkylthio, or is C(O)R₆ ; and R₆ is hydrogen, C₁-C₆ alkyl, C₃ -C₆ cycloalkyl or C₂ -C₆ alkynyl; or is C₁ -C₆ alkyl or C₃-C₆ cycloalkyl each substituted by halogen or by C₁ -C₄ alkoxy; or is C₂-C₆ alkenyl, or C₂ -C₆ alkenyl substituted by halogen; or is phenyl,benzyl, naphthyl or OR₁₂, or phenyl, benzyl or naphthyl each substitutedby halogen, C₁ -C₄ alkyl, C₁ -C₄ haloalkyl, C₁ -C₄ alkoxy, C₁ -C₄haloalkoxy, C₃ -C₆ alkenyloxy, C₃ -C₆ alkynyloxy nitro, cyano, COOR₁₃,NR₁₅ R₁₆, C(O)NR₁₇ R₁₈, X₁ R₂₀, SO₂ NR₂₁ R₂₂ or by X₂ R₂₃ ; R₁₂ is C₁-C₆ alkyl, C₁ -C₆ haloalkyl, oxetan-3-yl, or C₄ -C₆ cycloalkyl, whichmay for its part be substituted by halogen, C₁ -C₄ alkyl or by C₁ -C₄alkoxy; or is phenyl, benzyl or naphthyl, or phenyl, benzyl or naphthyleach substituted by C₁ -C₄ alkyl, C₁ -C₄ haloalkyl, C₁ -C₄ alkoxy, C₁-C₄ haloalkoxy, C₁ -C₄ alkylthio, C₁ -C₄ haloalkylthio, C₁ -C₄alkylsulfonyl, C₁ -C₄ alkylsulfinyl, nitro, cyano, COOR₂₇, NR₂₅ R₂₆,CONR₂₈ R₂₉ or by SO₂ NR₃₀ R₁₄ ; or is C₁ -C₆ alkyl substituted by C₁ -C₄alkoxy, C₃ -C₆ cycloalkyl, cyano, COOR₂₄ or by CONR₃₂ R₃₃ ; or is C₃ -C₆alkenyl, C₃ -C₆ haloalkenyl, C₃ -C₆ alkynyl, C₃ -C₆ -haloalkynyl, X₃ R₃₅or X₄ R₃₆ ; R₁₃ is hydrogen, C₁ -C₆ alkyl, C₃ -C₆ alkenyl, C₃ -C₆alkynyl or oxetan-3-yl; R₁₄, R₁₅, R₁₆, R₁₇, R₁₈, R₂₁, R₂₂, R₂₅, R₂₆,R₂₈, R₂₉, R₃₀, R₃₂ and R₃₃ are each independently of the othershydrogen, C₁ -C₄ alkyl, C₃ -C₆ alkenyl or C₃ -C₆ alkynyl; or R₁₅ and R₂₅are each independently of the other the groups --C(O)--X₅ --C₁ -C₄ alkylor --C(O)--C₁ -C₄ alkyl, which may for their part be substituted byhalogen; or R₁₅ and R₁₆ or R₁₇ and R₁₈ or R₂₁ and R₂₂ or R₂₅ and R₂₆ orR₂₈ and R₂₉ or R₃₀ and R₁₄ or R₃₂ and R₃₃ together form a C₄ -C₅alkylene chain, which may for its part be interrupted by oxygen or byNR₁₉, R₁₉ is hydrogen, C₁ -C₄ alkyl, C₃ -C₆ alkenyl or C₃ -C₆ alkynyl;R₂₀ and R₃₅ are each independently of the other C₁ -C₄ alkyl or C₁ -C₄haloalkyl; R₂₃ and R₃₆ are each independently of the other C₁ -C₄ alkylsubstituted by COOR₃₄ ; R₂₄, R₂₇ and R₃₄ are each independently of theother hydrogen or C₁ -C₄ alkyl; X₁ and X₃ are each independently of theother sulfur, SO or SO₂ ; X₂ and X₄ are each independently of the otheroxygen or sulfur; X₅ is oxygen or NR₃₇ ; and

R₃₇ is hydrogen, C₁ -C₄ alkyl, C₃ -C₆ alkenyl or C₃ -C₆ alkynyl; or anN-oxide or a salt of a compound of formula I, and

b) a herbicide-antagonistically effective amount of asulfamoylphenylurea of formula II ##STR4## wherein A₂ is a radical fromthe group ##STR5## R₇ and R₈ are each independently of the otherhydrogen, C₁ -C₈ alkyl, C₃ -C₈ cycloalkyl, C₃ -C₆ alkenyl, C₃ -C₆alkynyl or ##STR6## or are C₁ -C₄ alkyl substituted by C₁ -C₄ alkoxy orby ##STR7## R₇ and R₈ together form a C₄ -C₆ alkylene bridge, or a C₄-C₆ alkylene bridge interrupted by oxygen, sulfur, SO, SO₂, NH or by--N(C₁ -C₄ alkyl)--; R₉ is hydrogen or C₁ -C₄ alkyl; R₁₀ and R₁₁ areeach independently of the other hydrogen, halogen, cyano, nitro,trifluoromethyl, C₁ -C₄ alkyl, C₁ -C₄ alkoxy, C₁ -C₄ alkylthio, C₁ -C₄alkylsulfinyl, C₁ -C₄ alkylsulfonyl, --COOR_(j), CONR_(k) R_(m),--COR_(n), --SO₂ NR_(k) R_(m) or --OSO₂ --C₁ -C₄ alkyl; or R₁₀ and R₁₁together form a C₃ -C₄ alkylene bridge, which may be substituted byhalogen or by C₁ -C₄ alkyl, or a C₃ -C₄ alkenylene bridge, which may besubstituted by halogen or by C₃ - or C₄ -alkyl, or a butadienylenebridge, which may be substituted by halogen or by C₁ -C₄ alkyl, andR_(g) and R_(h) are each independently of the other hydrogen, halogen,C₁ -C₄ alkyl, trifluoromethyl, methoxy, methylthio or --COOR_(j) ; R_(c)is hydrogen, halogen, C₁ -C₄ alkyl or methoxy; R_(d) is hydrogen,halogen, nitro, C₁ -C₄ alkyl, C₁ -C₄ alkoxy, C₁ -C₄ alkylthio, C₁ -C₄alkylsulfinyl, C₁ -C₄ alkylsulfonyl, --COOR_(j) or --CONR_(k) R_(m) ;and R_(e) is hydrogen, halogen, halo-C₁ -C₄ alkyl, C₁ -C₄ alkyl,--COOR_(j), trifluoromethyl or methoxy; or R_(d) and R_(e) together forma C₃ -C₄ alkylene bridge;

R_(f) is hydrogen, halogen or C₁ -C₄ alkyl;

R_(x) and R_(y) are each independently of the other hydrogen, halogen,C₁ -C₄ alkyl, C₁ -C₄ -alkoxy, C₁ -C₄ alkylthio, --COOR₁₇,trifluoromethyl, nitro or cyano; R₁₇ is hydrogen, C₁ -C₁₀ alkyl, C₁ -C₄alkoxy-C₁ -C₄ alkyl, C₁ -C₄ alkylthio-C₁ -C₄ alkyl, di-C₁ -C₄alkylamino-C₁ -C₄ alkyl, halo-C₁ -C₈ alkyl, C₂ -C₈ alkenyl, halo-C₂ -C₈alkenyl, C₃ -C₈ alkynyl, C₃ -C₇ cycloalkyl, halo-C₃ -C₇ cycloalkyl, C₁-C₈ alkylcarbonyl, allylcarbonyl, C₃ -C₇ cycloalkylcarbonyl, benzoylthat is unsubstituted or mono- to tri-substituted in the phenyl ring bythe same or different substituents selected from halogen, C₁ -C₄ alkyl,halo-C₁ -C₄ alkyl, halo-C₁ -C₄ alkoxy and C₁ -C₄ alkoxy; or is furoyl orthienyl; or is C₁ -C₄ alkyl substituted by phenyl, halophenyl, C₁ -C₄alkylphenyl, C₁ -C₄ alkoxyphenyl, halo-C₁ -C₄ alkylphenyl, halo-C₁ -C₄alkoxyphenyl, C₁ -C₆ alkoxycarbonyl, C₁ -C₄ alkoxy-C₁ -C₈alkoxycarbonyl, C₃ -C₈ alkenyloxycarbonyl, C₃ -C₈ alkynyloxycarbonyl, C₁-C₈ alkylthiocarbonyl, C₃ -C₈ alkenylthiocarbonyl, C₃ -C₈alkynylthiocarbonyl, carbamoyl, mono-C₁ -C₄ alkylaminocarbonyl or bydi-C₁ -C₄ alkylaminocarbonyl; or is phenylaminocarbonyl that isunsubstituted or mono- to tri-substituted in the phenyl ring by the sameor different substituents selected from halogen, C₁ -C₄ alkyl, halo-C₁-C₄ alkyl, halo-C₁ -C₄ alkoxy and C₁ -C₄ alkoxy or that ismono-substituted in the phenyl ring by cyano or by nitro; or isdioxolan-2-yl that is unsubstituted or substituted by one or two C₁ -C₄alkyl radicals; or is dioxan-2-yl that is unsubstituted or substitutedby one or two C₁ -C₄ alkyl radicals; or is C₁ -C₄ alkyl that issubstituted by cyano, nitro, carboxy or by C₁ -C₈ alkylthio-C₁ -C₈alkoxycarbonyl; R_(j), R_(k) and R_(m) are each independently of theothers hydrogen or C₁ -C₄ alkyl; or R_(k) and R_(m) together form a C₄-C₆ alkylene bridge, or a C₄ -C₆ alkylene bridge interrupted by oxygen,NH or by --N(C₁ -C₄ alkyl)--; and R_(n) is C₁ -C₄ alkyl, phenyl, orphenyl substituted by halogen, C₁ -C₄ alkyl, methoxy, nitro or bytrifluoromethyl; or a salt of a compound of formula II.

The present invention relates also to the use of the compositionaccording to the invention in the control of weeds and grasses in cropsof useful plants, especially maize and sugar cane.

Halogen in the definitions is to be understood as being fluorine,chlorine, bromine and iodine, but preferably fluorine, chlorine andbromine, especially chlorine. Alkyl is to be understood as beingstraight-chain or branched alkyl; for example methyl, ethyl, n-propyl,isopropyl or the four isomers of butyl. Longer-chained alkyl groupsinclude the isomers of pentyl, hexyl, heptyl or octyl, the unbranchedchains being preferred in each case. Alkoxy is to be understood asbeing: methoxy, ethoxy, n-propoxy, isopropoxy or the four isomers of thebutoxy, pentyloxy and hexyloxy radicals, but especially methoxy, ethoxyor isopropoxy. Alkyl substituted by alkoxy is preferably methoxymethyl,ethoxymethyl, methoxyethyl and ethoxyethyl, but especially methoxyethyl.Alkyl that is substituted by unsubstituted or substituted phenyl ispreferably a derivative of phenylethyl or benzyl. Typical alkenyl andalkynyl radicals are allyl, 2-butenyl, methallyl, 3-butenyl, propargyl,2-butynyl, 3-butynyl or 2-pentenyl. Examples of cycloalkyl arecyclopropyl, cyclopentyl, cyclohexyl or cycloheptyl, but preferablycyclopentyl and cyclohexyl. Heterocycles are, for example, pyrrolidine,piperidine, pyrazolidine, imidazolidine, oxazolidine, thiazolidine,morpholine, thiomorpholine, piperazine or hexahydroazepine and also, inthe case of sulfur-containing rings, the oxidation products thereof. C₃-C₆ cycloalkyl interrupted by oxygen is, for example, oxetane, oxolane,oxane, oxepane or dioxane. In alkylthio, alkylsulfinyl or alkylsulfonyl,alkyl has the specific meanings listed above.

When substituents together form a C₃ -C₄ alkylene bridge, C₃ -C₄alkenylene bridge or butadienylene bridge, each of which may besubstituted by halogen or by C₁ -C₄ alkyl, there are formed, for exampletogether with a phenyl ring to which the bridge is attached, binuclearsystems, such as, for example, 1,2,3,4-tetrahydronaphthalene,1-chloro-2-methyl-3,4-dihydronaphthalene, indane,1,2-dihydronaphthalene, indene, naphthalene, 2-methylnaphthalene,1-n-butylnaphthalene, 2-ethylnaphthalene or 1-chloronaphthalene.

When substituents together form a C₃ - or C₄ -alkylene bridge, there areformed, together with the ring system to which they are attached,polynuclear systems, such as, for example, 2,3-tetramethylenethiophene,2,3-trimethylenethiophene, 2,3-tetramethylenefuran,3,4-tetramethylenepyridine or ##STR8## N-oxides of a compound of formulaI are to be understood as being compounds that comprise a group of theformula ##STR9## The invention relates also to the salts that can beformed by the compounds of formulae I and II with amines, alkali andalkaline earth metal bases or quaternary ammonium bases. Salt formationcan also be effected by the addition of a strong acid to the pyrimidinemoiety of the compound of formula I. Suitable acids for that purpose arehydrochloric acid, hydrobromic acid, sulfuric acid and nitric acid.

Of the alkali and alkaline earth metal hydroxides as salt-formingagents, special mention should be made of the hydroxides of lithium,sodium, potassium, magnesium and calcium, but especially those of sodiumand potassium.

Examples of amines suitable for ammonium cation formation are bothammonia and primary, secondary and tertiary C₁ -C₄ alkylamines, C₁ -C₄hydroxyalkylamines and C₂ -C₄ alkoxyalkylamines, for examplemethylamine, ethylamine, n-propylamine, isopropylamine, the four isomersof butylamine, n-amylamine, isoamylamine, hexylamine, heptylamine,octylamine, nonylamine, decylamine, pentadecylamine, hexadecylamine,heptadecylamine, octadecylamine, methyl-ethylamine,methyl-isopropylamine, methyl-hexylamine, methyl-nonylamine,methyl-pentadecylamine, methyl-octadecylamine, ethyl-butylamine,ethyl-heptylamine, ethyl-octylamine, hexyl-heptylamine,hexyl-octylamine, dimethylamine, diethylamine, di-n-propylamine,diisopropylamine, di-n-butylamine, di-n-amylamine, diisoamylamine,dihexylamine, diheptylamine, dioctylamine, ethanolamine,n-propanolamine, isopropanolamine, N,N-diethanolamine,N-ethylpropanolamine, N-butylethanolamine, allylamine,n-butenyl-2-amine, n-pentenyl-2-amine, 2,3-dimethylbutenyl-2-amine,dibutenyl-2-amine, n-hexenyl-2-amine, propylenediamine, diethanoiamine,trimethylamine, triethylamine, tri-n-propylamine, triisopropylamine,tri-n-butylamine, triisobutylamine, tri-sec-butylamine, tri-n-amylamine,methoxyethylamine and ethoxyethylamine; heterocyclic amines, such as,for example, pyridine, quinoline, isoquinoline, morpholine, piperidine,pyrrolidine, indoline, quinuclidine and azepine; primary arylamines,such as, for example, anilines, methoxyanilines, ethoxyanilines,o,m,p-toluidines, phenylenediamines, benzidines, naphthylamines ando,m,p-chloroanilines; but especially triethylamine, isopropylamine anddiisopropylamine.

Examples of quaternary ammonium bases are generally the cations ofhaloammonium salts, for example the tetramethylammonium cation, thetrimethylbenzylammonium cation, the triethylbenzylammonium cation, thetetraethylammonium cation, the trimethylethylammonium cation, and alsothe ammonium cation.

Preferably, R₆ is hydrogen, C₁ -C₆ alkyl, C₃ -C₆ cycloalkyl or C₂ -C₆alkynyl; or is C₁ -C₆ alkyl or C₃ -C₆ cycloalkyl each substituted byhalogen or by C₁ -C₄ alkoxy; or is C₂ -C₆ alkenyl, or C₂ -C₆ alkenylsubstituted by halogen.

In formula I in preferred compositions according to the invention, R₆ ishydrogen, C₁ -C₆ alkyl or C₃ -C₆ cycloalkyl, especially preferablyhydrogen or C₁ -C₆ alkyl. Also preferred are compositions according tothe invention in which compounds of formula I are used wherein R₃ is C₁-C₆ alkyl, or C₁ -C₆ alkyl that is mono- or poly-substituted by halogen,C₁ -C₆ alkoxy, C₃ -C₆ alkenyloxy, C₃ -C₆ alkynyloxy or by C₃ -C₆cycloalkyl, which may for its part be interrupted by oxygen; or is C₃-C₆ alkenyl, or C₃ -C₆ alkenyl that is mono- or poly-substituted byhalogen, C₁ -C₆ alkoxy, C₃ -C₆ alkenyloxy or by C₃ -C₆ alkynyloxy; or isC₄ -C₆ cycloalkyl, or C₄ -C₆ cycloalkyl that is mono- orpoly-substituted by halogen or by C₁ -C₆ alkoxy or may be interrupted byoxygen; or is C₃ -C₆ alkynyl, and R₆ is hydrogen or C₁ -C₆ alkyl.

Compounds of formula I preferred for use in the composition according tothe invention are also those wherein the pyridylsulfonylurea correspondsto the formula Ia ##STR10## wherein A, R, R₁ and R₂ are as defined underformula I.

Compositions according to the invention that comprise that compound offormula Ia together with a compound of formula IIf ##STR11## wherein R₈and R₉ are as defined under formula H and A₃ is the group ##STR12## areespecially preferred, R₈ and R₉ in formula IIf each being especiallyhydrogen or methyl.

Especially preferred among these compositions are those in which

a) R is hydrogen; or

b) A is --X--R₃ ; or

c) A is --N--(R₄)R₅ ; R₅ preferably being C(O)R₆.

In addition, valuable compositions according to the invention are thosein which a herbicide of formula Ia is used, wherein each of R and R₁ ishydrogen and A is difluoromethoxy or the group ##STR13## Especiallyoutstanding compositions comprise a compound of formula Ia wherein eachof R and R₁ is hydrogen and A is the group ##STR14## or --SO₂ --C₁ -C₄alkyl.

Compounds of formula II preferred for use in the composition accordingto the invention are those in which

A₂ is a radical of the formula ##STR15## wherein R_(g) and R_(h) areeach independently of the other hydrogen, halogen, C₁ -C₄ alkyl,trifluoromethyl, methoxy, methylthio or COOR_(j) ; R_(c) is hydrogen,halogen, C₁ -C₄ alkyl or methoxy; R_(d) is hydrogen, halogen, nitro, C₁-C₄ alkyl, C₁ -C₄ alkoxy, C₁ -C₄ alkylthio, C₁ -C₄ alkylsulfinyl, C₁ -C₄alkylsulfonyl, --COOR_(j) or --CONR_(k) R_(m) ; and R_(e) is hydrogen,halogen, C₁ -C₄ alkyl, --COOR_(j), trifluoromethyl or methoxy; or R_(d)and R_(e) together form a C₃ - or C₄ -alkylene bridge; R_(f) ishydrogen, halogen or C₁ -C₄ alkyl; R_(j), R_(k) and R_(m) are eachindependently of the others hydrogen or C₁ -C₄ alkyl; or R_(k) and R_(m)together form a C₄ -C₆ alkylene bridge, or a C₄ -C₆ alkylene bridgeinterrupted by oxygen, NH or by --N(C₁ -C₄ alkyl)--.

Of the above compounds of formula II, those wherein R_(c), R_(d), R_(e),R_(g) and R_(h) are each independently of the others hydrogen, C₁ -C₄alkyl or methoxy are especially preferred.

Further especially suitable groups of compounds of formula II are thosewherein each of R₁₀ and R₁₁ or each of R₈ and R₉ is hydrogen.

Special mention should also be made of those compounds of formula IIwherein each of R₉, R₁₀ and R₁₁ is hydrogen.

Especially valuable compositions according to the present invention arethose which comprise, as compound of formula I, a compound of formula Ia##STR16## wherein A, R, R₁, R₂ and R₃ are as defined under formula I;and, as compound of formula II, a compound of formula IIa ##STR17## orof formula IIb ##STR18## or of formula IIc ##STR19## or of formula IId##STR20## or of formula IIe ##STR21## The pyridylsulfonylureas offormula I used according to the invention either are known or can beprepared analogously to known methods. The preparation of such compoundsis described, for example, in EP-A-0 103 543, EP-A-0 459 949, EP-A-0 555770 and WO 92/16522. The sulfamoylphenylureas of formula II used for thecompositions according to the invention and the preparation of thoseureas are known, for example, from EP-A-0 365 484.

Other herbicidally active pyridylsulfonylureas especially suitable foruse in the composition according to the invention correspond to formulaIb ##STR22## wherein R, R₁, R₂, R₄ and R₆ are as defined under formulaI. Of these compounds of formula Ib, those in which R₆ is hydrogen or C₁-C₆ alkyl are preferred.

Also preferred are those compounds of formula Ib in which each of R andR₁ is hydrogen. Of particular value in that group are compounds in whicheach of R₄ and R₆ is methyl.

The compounds of formula Ib can be prepared as follows:

a) a pyridylsulfonamide of formula III ##STR23## wherein R, R₄ and R₆are as defined under formula I, is reacted in the presence of a basewith a N-pyrimidinyl carbamate of formula IV ##STR24## wherein R₁ and R₂are as defined under formula I and R₁₈ is C₁ -C₄ alkyl, or is phenylwhich may be substituted by C₁ -C₄ alkyl or by halogen; or

b) a 2-pyridylsulfonyl chloride of formula VII ##STR25## wherein R, R₄and R₆ are as defined under formula I, is reacted in the presence of abase and in an inert, organic solvent with a metal cyanate of formulaVIII

    O═C═N⊖M⊕                               (VIII),

wherein M⊕ is an ammonium, phosphonium, sulfonium or an alkali metalcation, and with a 2-aminopyrimidine of formula IX ##STR26## wherein R₁and R₂ are as defined under formula I, or c) a pyridylsulfonamide offormula III ##STR27## wherein R, R₄ and R₆ are as defined under formulaI, is reacted in the presence of a base with a 2-pyrimidinyl isocyanateof formula X ##STR28## wherein R₂ is as defined under formula I.

The reactions to form compounds of formula Ib are advantageously carriedout in aprotic, inert organic solvents. Such solvents are hydrocarbons,such as benzene, toluene, xylene or cyclohexane, chlorinatedhydrocarbons, such as dichloromethane, trichloromethane,tetrachloromethane or chlorobenzene, ethers, such as diethyl ether,ethylene glycol dimethyl ether, diethylene glycol dimethyl ether,tetrahydrofuran or dioxane, nitriles, such as acetonitrile orpropionitrile, amides, such as dimethylformamide, diethylformamide orN-methylpyrrolidinone. The reaction temperatures are preferably from-20° to +120° C.

The reactions are generally slightly exothermic and can be carried outat room temperature. It is expedient to heat the reaction mixturebriefly to boiling point in order to reduce the reaction time or also toinitiate the reaction. The reaction times can also be reduced by addinga few drops of base as a reaction catalyst. Suitable bases areespecially tertiary amines, such as trimethylamine, triethylamine,quinuclidine, 1,4-diazabicyclo[2.2.2]octane,1,5-diazabicyclo[4.3.0]non-5-ene or 1,5-diazabicyclo[5.4.0]undec-7-ene.The bases used may, however, also be inorganic bases, such as hydrides,such as sodium or calcium hydride, hydroxides, such as sodium andpotassium hydroxide, carbonates, such as sodium and potassium carbonate,or hydrogen carbonates, such as potassium and sodium hydrogen carbonate.

The end products of formula Ib can be isolated by concentration and/orevaporation of the solvent and purified by recrystallisation ortrituration of the solid residue in solvents in which they are notreadily soluble, such as ethers, aromatic hydrocarbons or chlorinatedhydrocarbons.

The 2-pyrimidinyl isocyanates of formula X can be prepared from thecorresponding 2-aminopyrimidines by known methods. Such methods aredescribed, for example, in U.S. Pat. No. 3,919,228 and in U.S. Pat. No.3,732,223.

The intermediates of formula IV can be prepared analogously to knownprocesses. The compounds of formula III are known or can be prepared byknown methods. Compounds of formula III are known, for example, fromEP-A-0 555 770 and can also be prepared analogously to the processesdescribed in EP-A-0 314 505 and EP-A-0 459 949. Processes for thepreparation of N-pyrimidinyl carbamates are described, for example, inEP-A-0 101 670.

Compounds of formula III can be prepared, for example, by reacting acompound of formula V ##STR29## wherein R and R₄ are as defined underformula I, in the presence of a base, with an acylating agent of formulaVI

    Z--R.sub.5                                                 (VI),

wherein R₅ is the group C(O)--R₆, R₆ is as defined under formula I and Zis a leaving group, such as, for example, halogen, R₅ O--, R₆ C(O)O-- orimidazole. Such reactions are described, for example, in Farmaco Ed.scient. 12, 392 (1957). The compounds of formula V either are known orcan be prepared by known methods which are disclosed, for example, inEP-A-0 459 949.

Pyridylsulfonamides of formula III can also be prepared from thecorresponding 2-pyridylsulfonyl chlorides of formula VII by reactionwith ammonia.

2-pyridylsulfonyl chlorides of formula VII can be prepared veryespecially advantageously by reacting a compound of formula XI ##STR30##wherein R, R₄ and R₆ are as defined under formula I and R₃₈ is benzyl,methoxymethyl or isopropyl, with aqueous chlorine.

The compounds of formula XI are novel and the present invention relatesalso to those compounds. The intermediates of formula XI developedspecifically for the present invention permit an economically especiallyadvantageous preparation of the compounds of formulae VII and III, whichare required for the preparation of the herbicide of formula Ib whichpreferred compositions according to the invention comprise.

The compounds of formula XI are prepared by reacting a compound offormula XII ##STR31## wherein R, R₄ and R₃₈ are as defined above, in thepresence of a base, with a compound of formula VI

    Z--R.sub.5                                                 (VI),

wherein R₅ is the group C(O)--R₆, R₆ is as defined under formula I and Zis a leaving group, such as, for example, halogen, R₅ O--, R₆ C(O)O-- orimidazole.

Compounds of formula XII can be prepared by reacting, for example, acompound of formula XIV ##STR32## wherein R is as defined under formulaI, with benzyl mercaptan or isopropyl mercaptan in the presence of abase to form a compound of formula XIII ##STR33## wherein R₃₈ is benzyl,methoxymethyl or isopropyl and R is as deemed under formula I, andconverting the latter in the presence of a base into a compound offormula XII by reaction with a compound of formula XV

    H.sub.2 NR.sub.4                                           (XV),

wherein R₄ is as defined under formula I.

The invention relates also to a method of selectively controlling weedsin crops of useful plants, which comprises treating the useful plants orthe crop area thereof with a herbicidally effective amount of apyridylsulfonylurea of formula I and a herbicide-antagonisticallyeffective amount of a sulfamoylphenylurea of formula II, simultaneouslyor independently of one another.

Cultivated plants that can be protected against the harmful effect ofthe above-mentioned herbicides of formula I are especially those thatare of importance in the fields of food and textiles, for example sugarcane and, especially, sorghum and maize, and also rice and other speciesof cereal, such as wheat, rye, barley and oats. The compositionaccording to the invention is especially suitable for protecting maizecrops and sugar cane crops against the herbicidal action of thecompounds of formula I.

The weeds to be controlled may be both monocots and dicots.

There come into consideration as cultivated plants or parts of thoseplants, for example, those mentioned above. Crop areas are areas of landon which the cultivated plants are already growing or in which the seedsof those cultivated plants have been sown, and also areas of land onwhich it is intended to grow those cultivated plants.

A safener of formula II may, depending on the purpose, be used topre-treat the seed material of the cultivated plant (dressing the seedor the seedlings) or may be incorporated into the soil before or aftersowing. It may, however, also be applied, alone or together with theherbicide, after the emergence of the plants. The treatment of theplants or seed with the safener can therefore, in principle, be effectedindependently of the time at which the herbicide is applied. Thetreatment of the plant can, however, also be carried out by applying theherbicide and the safener simultaneously (for example in the form of atank mixture).

The rate of application of the safener in relation to the herbicidedepends largely on the method of application. In the case of fieldtreatment, which is effected either using a tank mixture with acombination of the safener and the herbicide or by the separateapplication of the safener and the herbicide, the ratio of safener toherbicide is generally from 1:100 to 1:1, preferably from 1:20 to 1:1,and especially 1:1. In contrast, in the case of seed dressing, muchsmaller amounts of safener are required in relation to the rate ofapplication of herbicide per hectare of crop area.

In the case of field treatment, from 0.001 to 5.0 kg safener/ha,preferably from 0.005 to 0.5 kg safener/ha, are generally applied.

The rate of application of herbicide is generally from 0.001 to 2 kg/ha,but preferably from 0.001 to 0.5 kg/ha.

In the case of seed dressing, from 0.001 to 10 g safener/kg seed,preferably from 0.05 to 2 g safener/kg seed are generally applied. Ifthe safener is applied in liquid form by seed soaking shortly beforesowing, then it is advantageous to use safener solutions that comprisethe active ingredient in a concentration of from 1 to 10 000, preferablyfrom 100 to 1000 ppm.

For the purpose of application, the compounds of formula II orcombinations of compounds of formula II and the herbicides to beantagonism are advantageously used together with the adjuvantsconventionally employed in formulation technology, and are thereforeformulated in known manner e.g. into emulsifiable concentrates, coatablepastes, directly sprayable or dilutable solutions, dilute emulsions,wettable powders, soluble powders, dusts, granules, and alsoencapsulations in e.g. polymer substances. As with the nature of thecompositions to be used, the methods of application, such as spraying,atomising, dusting, scattering, coating or pouring, are chosen inaccordance with the intended objectives and the prevailingcircumstances.

The formulations, i.e. the compositions, preparations or mixturescomprising the compound (active ingredient) of formula II or acombination of the compound of formula II and the herbicide of formula Ito be antagonised and, where appropriate, a solid or liquid adjuvant,are prepared in known manner, e.g. by homogeneously mixing and/orgrinding the active ingredients with extenders, e.g. solvents, solidcarriers and, where appropriate, surface-active compounds (surfactants).

Suitable solvents are: aromatic hydrocarbons, preferably the fractionscontaining 8 to 12 carbon atoms, such as xylene mixtures or substitutednaphthalenes, phthalic acid esters, such as dibutyl or dioctylphthalate, aliphatic hydrocarbons such as cyclohexane or paraffins,alcohols and glycols and their ethers and esters, such as ethanol,ethylene glycol, ethylene glycol monomethyl or monoethyl ether, ketonessuch as cyclohexanone, strongly polar solvents such asN-methyl-2-pyrrolidone, dimethyl sulfoxide or dimethylformamide, andalso vegetable oils or epoxidised vegetable oils, such as epoxidisedcoconut oil or soybean oil; or water.

The solid carriers used, e.g. for dusts and dispersible powders, arenormally natural mineral fillers such as calcite, talcum, kaolin,montmorillonite or attapulgite. In order to improve the physicalproperties it is also possible to add highly dispersed silicic acid orhighly dispersed absorbent polymers. Suitable granulated adsorptivecarriers are porous types, for example pumice, broken brick, sepioliteor bentonite; and suitable nonsorbent carriers are, for example, calciteor sand. In addition, a great number of pregranulated materials ofinorganic or organic nature can be used, e.g. especially dolomite orpulverised plant residues.

Depending on the nature of the compound of formula II to be formulated,and, where appropriate, also the herbicide of formula I to beantagonised, suitable surface-active compounds are non-ionic, cationicand/or anionic surfactants having good emulsifying, dispersing andwetting properties. The term "surfactants" will also be understood ascomprising mixtures of surfactants.

Both so-called water-soluble soaps and water-soluble syntheticsurface-active compounds are suitable anionic surfactants.

Suitable soaps are the alkali metal salts, alkaline earth metal salts orunsubstituted or substituted ammonium salts of higher fatty acids (C₁₀-C₂₂), e.g. the sodium or potassium salts of oleic or stearic acid, orof natural fatty acid mixtures which can be obtained e.g. from coconutoil or tallow oil. Mention may also be made of fatty acid methyltaurinsalts.

More frequently, however, so-called synthetic surfactants are used,especially fatty sulfonates, fatty sulfates, sulfonated benzimidazolederivatives or alkylarylsulfonates.

The fatty sulfonates or sulfates are usually in the form of alkali metalsalts, alkaline earth metal salts or unsubstituted or substitutedammonium salts and contain a C₈ -C₂₂ alkyl radical, which also includesthe alkyl moiety of acyl radicals, e.g. the sodium or calcium salt oflignosulfonic acid, of dodecyl sulfate or of a mixture of fatty alcoholsulfates obtained from natural fatty acids. These compounds alsocomprise the salts of sulfated and sulfonated fatty alcohol/ethyleneoxide adducts. The sulfonated benzimidazole derivatives preferablycontain 2 sulfonic acid groups and one fatty acid radical containing 8to 22 carbon atoms. Examples of alkylarylsulfonates are the sodium,calcium or triethanolamine salts of dodecylbenzenesulfonic acid,dibutylnaphthalenesulfonic acid, or of a condensate ofnaphthalenesulfonic acid and formaldehyde.

Also suitable are corresponding phosphates, e.g. salts of the phosphoricacid ester of an adduct of p-nonylphenol with 4 to 14 mol of ethyleneoxide, or phospholipids.

Non-ionic surfactants are preferably polyglycol ether derivatives ofaliphatic or cycloaliphatic alcohols, saturated or unsaturated fattyacids and alkylphenols, said derivatives containing 3 to 30 glycol ethergroups and 8 to 20 carbon atoms in the (aliphatic) hydrocarbon moietyand 6 to 18 carbon atoms in the alkyl moiety of the alkylphenols.

Further suitable non-ionic surfactants are the water-soluble adducts ofpolyethylene oxide with polypropylene glycol,ethylenediaminopolypropylene glycol and alkylpolypropylene glycolcontaining 1 to 10 carbon atoms in the alkyl chain, which adductscontain 20 to 250 ethylene glycol ether groups and 10 to 100 propyleneglycol ether groups. These compounds usually contain 1 to 5 ethyleneglycol units per propylene glycol unit.

Representative examples of non-ionic surfactants arenonylphenolpolyethoxyethanols, castor oil polyglycol ethers,polypropylene/polyethylene oxide adducts,tributylphenoxypolyethoxyethanol, polyethylene glycol andoctylphenoxypolyethoxyethanol.

Fatty acid esters of polyoxyethylene sorbitan, e.g. polyoxyethylenesorbitan trioleate, are also suitable non-ionic surfactants.

Cationic surfactants are preferably quaternary ammonium salts whichcontain, as N-substituent, at least one C₈ -C₂₂ alkyl radical and, asfurther substituents, unsubstituted or halogenated lower alkyl, benzylor hydroxy-lower alkyl radicals. The salts are preferably in the form ofhalides, methyl sulfates or ethyl sulfates, e.g.stearyltrimethylammonium chloride orbenzyldi(2-chloroethyl)ethylammonium bromide.

The surfactants customarily employed in formulation technology aredescribed inter alia in the following publications:

"Mc Cutcheon's Detergents and Emulsifiers Annual" MC Publishing Corp.,Ridgewood, N.J., 1981. Stache, H., "Tensid-Taschenbuch", Carl HanserVerlag, Munich/Vienna, 1981.

The agrochemical compositions generally comprise 0.1 to 99% by weight,preferably 0.1 to 95% by weight, of a compound of formula II or amixture of antidote and herbicide, 1 to 99.9% by weight, preferably 5 to99.8% by weight, of a solid or liquid adjuvant and 0 to 25% by weight,preferably 0.1 to 25% by weight, of a surfactant.

Whereas commercial products will preferably be formulated asconcentrates, the end user will normally employ dilute formulations.

The compositions may also comprise further ingredients such asstabilisers, antifoams, viscosity regulators, binders and tackifiers, aswell as fertilisers or other active ingredients for obtaining specialeffects.

There are various suitable methods and techniques for using thecompounds of formula II or the compositions comprising them forprotecting cultivated plants against the harmful effects of herbicidesof formula I; the following are examples:

i) Seed dressing

a) Dressing the seeds with a wettable powder formulation of a compoundof formula II by shaking in a vessel until the formulation is uniformlydistributed over the seed surface (dry dressing). Approximately from 1to 500 g of compound of formula II (from 4 g to 2 kg of wettable powder)are used per 100 kg of seed.

b) Dressing the seeds with an emulsifiable concentrate of a compound offormula II according to method a) (wet dressing).

c) Dressing by immersing the seed in a mixture comprising from 100 to1000 ppm of compound of formula II for from 1 to 72 hours and, ifdesired, subsequently drying the seeds (immersion dressing).

Dressing the seed or treating the germinated seedlings are naturally thepreferred methods of application because the treatment with the activeingredient is directed wholly at the target crop. Generally from 1 to1000 g of antidote, preferably from 5 to 250 g of antidote, are used per100 kg of seed, although, depending on the method employed, which alsoallows the addition of other active ingredients or micronutrients,amounts that exceed or fall short of the specified concentration limitsmay be employed (repeat dressing).

ii) Application from a tank mixture

A liquid formulation of a mixture of antidote and herbicide (ratio ofthe one to the other from 10:1 to 1:100) is used, the rate ofapplication of herbicide being from 0.01 to 5.0 kg per hectare. Such atank mixture is applied before or after sowing.

iii) Application to the seed furrow

The antidote is introduced into the open, sown seed furrow in the formof an emulsifiable concentrate, a wettable powder or granules and, afterthe seed furrow has been covered, the herbicide is applied preemergencein the normal manner.

iv) Controlled release of the active ingredient

The compound of formula II is applied in solution to mineral granulatedcarriers or polymerised granules (urea/formaldehyde) and dried. Ifdesired, a coating may be applied (coated granules) which enables theactive ingredient to be released in metered amounts over a predeterminedperiod of time.

The compounds of formulae I and II may be formulated either separatelyor together. Preferred formulations have especially the followingcomposition (throughout, percentages are by weight):

    ______________________________________                                        Emulsifiable concentrates:                                                    active ingredient:                                                                            1 to 20%, preferably 5 to 10%                                 surface-active agent:                                                                         5 to 30%, preferably 10 to 20%                                liquid carrier: 15 to 94%, preferably 70 to 85%                               Dusts:                                                                        active ingredient:                                                                            0.1 to 10%, preferably 0.1 to 1%                              solid carrier:  99.9 to 90%, preferably 99.9 to 99%                           Suspension concentrates:                                                      active ingredient:                                                                            5 to 75%, preferably 10 to 50%                                water:          94 to 24%, preferably 88 to 30%                               surface-active agent:                                                                         1 to 40%, preferably 2 to 30%                                 Wettable powders:                                                             active ingredient:                                                                            0.5 to 90%, preferably 1 to 80%                               surface-active agent:                                                                         0.5 to 20%, preferably 1 to 15%                               solid carrier:  5 to 95%, preferably 15 to 90%                                Granules:                                                                     active ingredient:                                                                            0.5 to 30%, preferably 3 to 15%                               solid carrier:  99.5 to 70%, preferably 97 to 85%                             ______________________________________                                    

Preparation Examples Example P1: Preparation of3-(N-methyl-N-methylcarbonylamino)-pyridin-2-yl-sulfonamide ##STR34##0.89 ml of pyridine and 0.82 ml of acetyl bromide are added insuccession at room temperature to a solution of 1.87 g of3-N-methylaminopyridin-2-yl-sulfonamide in 40 ml of dry acetonitrile.After 30 minutes a further 0.3 ml of acetyl bromide is added. Afterstirring for 60 minutes, 0.32 ml of pyridine is added. After stirringfor 30 minutes, the reaction mixture is filtered to give 0.8 g of3-(N-methyl-N-methylcarbonylamino)pyridin-2-yl-sulfonamide which has amelting point of from 181° to 185° C. Example P2: Preparation ofN-(N-methyl-N-methylcarbonylamino)-pyridin-2-yl-sulfonyl-N'-(4-methoxy-6-methylpyrimidin-2-yl)urea(Compound No. 1.02) ##STR35## 2.18 ml of1,5-diazabicyclo[5.4.0]undec-5-ene and 3.89 g ofN-(4-methoxy-6-methyl-pyrimidin-2-yl)-phenyl carbamate are added insuccession to a solution of 3.07 g of3-(N-methyl-N-methylcarbonylamino)-pyridin-2-yl-sulfonamide in 50 ml ofacetonitrile. After stirring for 45 minutes, the reaction mixture isconcentrated in vacuo, the oily residue is triturated with 10 ml of 2Nhydrochloric acid and then diluted with 10 ml of water. The crystallineproduct is filtered and then washed with water and diethyl ether to give5.25 g ofN-(N-methyl-N-methylcarbonylamino)-pyridin-2-yl-sulfonyl-N'-(4-methoxy-6-methylpyrimidin-2-yl)urea(Compound No. 1.01 ) which has a melting point of from 182° to 184° C.Example P3: Preparation of3-(N-methyl-N-methylcarbonylamino)-pyridin-2-yl-sulfonyl chloride##STR36## 4.6 g of chlorine gas are introduced over a period of 15minutes at a temperature of -5° C. into an emulsion of 3.6 g of3-(N-methyl-N-methylcarbonylamino)-2-isopropylthiopyridine in 35 ml ofmethylene chloride and 48 ml of 1N hydrochloric acid and the batch isstirred for a further 15 minutes. Nitrogen is then passed through thereaction mixture over a period of 20 minutes at the same temperature.After separating the phases and washing three times with methylenechloride and ice-water, the reaction mixture is dried with sodiumsulfate and filtered. The resulting solution ofN-(N-methyl-N-methyl-carbonylamino)-pyridin-2-yl-sulfonyl chloride (60ml) can be reacted directly either to form the corresponding sulfonamide(Example P1) or to form the sulfonylureas of formula I wherein R ishydrogen and each of R₄ and R₆ is methyl. Example P4: Preparation of3-(N-methyl-N-methylcarbonylamino)-2-isopropylthiopyridine ##STR37##1.34 ml of acetyl bromide are added dropwise at a temperature of from 0°to 2° C. to a solution of 2.73 g of 3-N-methyl-2-isopropylthiopyridinein 40 ml of acetonitrile. The reaction mixture is then stirred for 20minutes at 0° C. After adding 1.33 ml of pyridine and stirring for onehour, the reaction mixture is concentrated and ethyl acetate/water isadded.

After washing 3 times with ethyl acetate and once with water, thereaction mixture is dried over sodium sulfate and then concentrated byevaporation to give 3.25 g ofN-(N-methyl-N-methylcarbonylamino)-2-isopropylthiopyridine which, afterrecrystallisation from petroleum ether, has a melting point of from 49°to 51 ° C.

Example P5: Preparation of 3-N-methylamino-2-isopropylthiopyridine##STR38## 45 g of methylamine gas are added under pressure to 8.56 g of3-fluoro-2-isopropylthiopyridine in a pressure vessel and the reactionmixture is maintained at a temperature of 140° C. for 24 hours and thenat 150° C. for 16 hours. After filtering and concentrating the reactionmixture by evaporation, purification is effected by columnchromatography (ethyl acetate/hexane 1:9) to give 6.77 g of3-N-methylamino-2-isopropylthiopyridine which has a melting point offrom 37° to 38° C. Example P6: Preparation of3-fluoro-2-isopropylthiopyridine ##STR39## 220.93 g of isopropylmercaptan are added dropwise at a temperature of from 0° to -5° C. to amixture of 388.6 g of potassium carbonate and 301 g of2,3-difluoropyridine in 4300 ml of dimethylformamide. After stirring for20 minutes, the temperature of the reaction mixture is allowed to riseslowly to room temperature and is stirred for a further 30 minutes. Thereaction mixture is then added to an ice-water/ethyl acetate mixture,the phases are washed four times with ethyl acetate and ice-water andthen dried over sodium sulfate. After filtering and concentrating byevaporation, the resulting crude product (510 g) is purified by columnchromatography (ethyl acetate/hexane 1:9) to give 327.3 g of3-fluoro-2-isopropylthiopyridine in the form of an oil.

The compounds of formulae I, Ib and III listed in the following Tablesare prepared in an analogous manner.

                                      TABLE 1                                     __________________________________________________________________________    Compounds of formula Ib                                                        ##STR40##                                      (Ib)                          Comp.                                                                         No.   R     R.sub.4                                                                             R.sub.6         R.sub.1                                                                           R.sub.2                                                                             m.p. [°C.]                 __________________________________________________________________________    1.01  H     CH.sub.3                                                                            CH.sub.3        H   OCH.sub.3                                                                           178-180                           1.02  H     CH.sub.3                                                                            CH.sub.3        H   CH.sub.3                                                                            182-184                           1.03  H     H     CH.sub.3        H   OCH.sub.3                                                                           162-164                           1.04  H     H     CH.sub.3        H   OCH.sub.3                                                                           151-152                           1.05  6-CH.sub.3                                                                          CH.sub.3                                                                            CH.sub.3        H   OCH.sub.3                               1.06  6-CH.sub.3                                                                          CH.sub.3                                                                            CH.sub.3        H   CH.sub.3                                1.07  H     C.sub.2 H.sub.5                                                                     CH.sub.3        H   OCH.sub.3                               1.08  H     C.sub.3 H.sub.7 -(i)                                                                CH.sub.3        H   OCH.sub.3                               1.09  H     H     CHCl.sub.2      H   OCH.sub.3                               1.10  H     H     CHCl.sub.2      H   CH.sub.3                                1.11  6-CH.sub.3                                                                          CH.sub.3                                                                            CHCl.sub.2      H   OCH.sub.3                               1.12  H     H     CHCl.sub.2      H   CH.sub.3                                1.13  H     H     CH.sub.2 Cl     H   CH.sub.3                                1.14  H     H     CH.sub.2 Cl     H   OCH.sub.3                               1.15  H     H     CF.sub.3        H   OCH.sub.3                               1.16  H     H     CF.sub.3        H   CH.sub.3                                1.17  H     CH.sub.3                                                                            CF.sub.3        H   CH.sub.3                                1.18  H     CH.sub.3                                                                            CF.sub.3        H   OCH.sub.3                               1.19  6-CH.sub.3                                                                          CH.sub.3                                                                            CF.sub.3        H   OCH.sub.3                               1.20  6-CH.sub.3                                                                          H     H               H   OCH.sub.3                               1.21  6-CH.sub.3                                                                          CH.sub.3                                                                            H               H   OCH.sub.3                               1.22  H     H     H               H   OCH.sub.3                               1.23  H     H     H               H   CH.sub.3                                1.24  H     H     CH.sub.2CH.sub.2                                                                              H   CH.sub.3                                1.25  H     CH.sub.3                                                                            CH.sub.2CH.sub.2                                                                              H   OCH.sub.3                                                                           163-165                           1.26  H     H                                                                                    ##STR41##      H   CH.sub.3                                1.27  H     H                                                                                    ##STR42##      H   OCH.sub.3                               1.28  H     H                                                                                    ##STR43##      H   OCH.sub.3                               1.29  H     H                                                                                    ##STR44##      H   CH.sub.3                                1.30  H     H                                                                                    ##STR45##      H   CH.sub.3                                1.31  H     CH.sub.3                                                                             ##STR46##      H   OCH.sub.3                               1.32  6-CH.sub.3                                                                          CH.sub.3                                                                             ##STR47##      H   OCH.sub.3                               1.33  H     H                                                                                    ##STR48##      H   OCH.sub.3                                                                           150-152                           1.34  H     CH.sub.3                                                                             ##STR49##      H   OCH.sub.3                               1.35  H     CH.sub.3                                                                             ##STR50##      H   CH.sub.3                                1.36  H     CH.sub.3                                                                             ##STR51##      H   OCH.sub.3                               1.37  H     H                                                                                    ##STR52##      H   OCH.sub.3                                                                           181-183                           1.38  6-CH.sub.3                                                                          H                                                                                    ##STR53##      H   OCH.sub.3                               1.39  6-CH.sub.3                                                                          CH.sub.3                                                                             ##STR54##      H   OCH.sub.3                               1.40  H     CH.sub.3                                                                             ##STR55##      H   OCH.sub.3                                                                           187-189                           1.41  H     CH.sub.3                                                                             ##STR56##      H   OCH.sub.3                                                                           168-170                           1.42  6-CH.sub.3                                                                          CH.sub.3                                                                             ##STR57##      H   OCH.sub.3                               1.43  H     CH.sub.3                                                                             ##STR58##      H   CH.sub.3                                1.44  H     H                                                                                    ##STR59##      H   OCH.sub.3                               1.45  H     CH.sub.3                                                                             ##STR60##      H   OCH.sub.3                                                                           179-182                           1.46  H     CH.sub.3                                                                             ##STR61##      H   OCH.sub.3                               1.47  H     H                                                                                    ##STR62##      H   OCH.sub.3                               1.48  H     CH.sub.3                                                                             ##STR63##      H   CH.sub.3                                1.49  H     CH.sub.3                                                                             ##STR64##      H   OCH.sub.3                               1.50  H     CH.sub.3                                                                             ##STR65##      H   CH.sub.3                                1.51  H     H                                                                                    ##STR66##      H   CH.sub.3                                1.52  H     H                                                                                    ##STR67##      H   CH.sub.3                                1.53  H     H                                                                                    ##STR68##      H   CH.sub.3                                1.54  H     H                                                                                    ##STR69##      H   OCH.sub.3                               1.55  H     CH.sub.3                                                                             ##STR70##      H   OCH.sub.3                               1.56  H     CH.sub.3                                                                             ##STR71##      H   CH.sub.3                                1.57  H     CH.sub.3                                                                             ##STR72##      H   CH.sub.3                                1.58  H     CH.sub.3                                                                             ##STR73##      H   OCH.sub.3                               1.59  H     CH.sub.3                                                                            OCH.sub.3       H   OCH.sub.3                               1.60  H     CH.sub.3                                                                            OC.sub.2 H.sub.5                                                                              H   OCH.sub.3                                                                           160-163                           1.61  H     CH.sub.3                                                                            OC.sub.2 H.sub.5                                                                              H   CH.sub.3                                1.62  H     H     OC.sub.2 H.sub.5                                                                              H   OCH.sub.3                               1.63  H     CH.sub.3                                                                            CH.sub.2 Cl     H   OCH.sub.3                                                                           182-184                           1.64  H     CH.sub.3                                                                            CH.sub.2 Cl     H   CH.sub.3                                1.65  H     CH.sub.3                                                                            CHCl.sub.2      H   CH.sub.3                                1.66  H     CH.sub.3                                                                            CHCl.sub.2      H   OCH.sub.3                                                                           180-182                           1.67  H     CH.sub.3                                                                             ##STR74##      H   OCH.sub.3                                                                           142-144                           1.68  H     H                                                                                    ##STR75##      H   OCH.sub.3                               1.69  H     CH.sub.3                                                                             ##STR76##      H   OCH.sub.3                                                                           177-179                           1.70  H     CH.sub.3                                                                             ##STR77##      H   CH.sub.3                                1.71  H     H                                                                                    ##STR78##      H   OCH.sub.3                               1.72  H     H                                                                                    ##STR79##      H   OCH.sub.3                               1.73  H     CH.sub.3                                                                             ##STR80##      H   OCH.sub.3                                                                           188-190                           1.74  H     CH.sub.3                                                                             ##STR81##      H   CH.sub.3                                1.75  H     CH.sub.3                                                                             ##STR82##      H   OCH.sub.3                               1.76  H     H                                                                                    ##STR83##      H   OCH.sub.3                               1.77  H     CH.sub.3                                                                             ##STR84##      H   OCH.sub.3                               1.78  H     CH.sub.3                                                                            CH.sub.3 CCl.sub.2                                                                            H   OCH.sub.3                               1.79  H     CH.sub.3                                                                             ##STR85##      H   OCH.sub.3                               1.80  H     CH.sub.3                                                                             ##STR86##      H   CH.sub.3                                                                            195-198                           1.81  H     CH.sub.3                                                                             ##STR87##      H   CH.sub.3                                1.82  H     CH.sub.3                                                                             ##STR88##      H   OCH.sub.3                                                                           192-195                           1.83  H     CH.sub.3                                                                             ##STR89##      H   OCH.sub.3                                                                           190-193                           1.84  H     CH.sub.3                                                                             ##STR90##      H   OCH.sub.3                               1.85  H     CH.sub.3                                                                             ##STR91##      H   OCH.sub.3                               1.86  H     H                                                                                    ##STR92##      H   OCH.sub.3                               1.87  H     CH.sub.3                                                                             ##STR93##      H   OCH.sub.3                               1.88  H     CH.sub.3                                                                             ##STR94##      H   OCH.sub.3                                                                           180-182                           1.89  H     CH.sub.3                                                                            (CH.sub.3).sub.2 CHO                                                                          H   OCH.sub.3                               1.90  H     CH.sub.3                                                                             ##STR95##      H   OCH.sub.3                               1.91  H     CH.sub.3                                                                             ##STR96##      H   OCH.sub.3                               1.92  H     H                                                                                    ##STR97##      H   OCH.sub.3                               1.93  H     H                                                                                    ##STR98##      H   OCH.sub.3                               1.94  H     CH.sub.3                                                                             ##STR99##      H   OCH.sub.3                               1.95  H     CH.sub.3                                                                             ##STR100##     H   OCH.sub.3                               1.96  H     CH.sub.3                                                                             ##STR101##     H   OCH.sub.3                               1.97  H     CH.sub.3                                                                            C.sub.2 H.sub.5 H   OCH.sub.3                                                                           171-173                           1.98  H     CH.sub.3                                                                            CH.sub.2 OCH.sub.3                                                                            H   OCH.sub.3                                                                           180-182                           1.99  H     CH.sub.3                                                                            H               H   OCH.sub.3                                                                           175-177                           1.100 H     CH.sub.3                                                                            H               H   CH.sub.3                                                                            163-165                           1.101 H     C.sub.2 H.sub.5                                                                     H               H   OCH.sub.3                                                                           176-177                           1.102 H     C.sub.2 H.sub.5                                                                     H               H   OCH.sub.3                                                                           192-155                           __________________________________________________________________________

                                      TABLE 2                                     __________________________________________________________________________    Compounds of formula III:                                                                                          (III)                                     ##STR102##                                                                   Comp.                                                                         No.   R     R.sub.4                                                                            R.sub.6         m.p. [°C.]                            __________________________________________________________________________    2.01  H     H    CH.sub.3        172-174                                      2.02  H     CH.sub.3                                                                           CH.sub.3        181-185                                      2.03  6-CH.sub.3                                                                          CH.sub.3                                                                           CH.sub.3                                                     2.04  H     H    CHCl.sub.2      190-192                                      2.05  6-CH.sub.3                                                                          CH.sub.3                                                                           CHCl.sub.2                                                   2.06  H     CH.sub.3                                                                           CH.sub.2 Cl                                                  2.07  H     H    CF.sub.3                                                     2.08  H     CH.sub.3                                                                           CF.sub.3                                                     2.09  6-CH.sub.3                                                                          CH.sub.3                                                                           CF.sub.3                                                     2.10  6-CH.sub.3                                                                          H    H                                                            2.11  6-CH.sub.3                                                                          CH.sub.3                                                                           H                                                            2.12  H     CH.sub.3                                                                           H               120-122                                      2.13  H     CH.sub.3                                                                           CH.sub.2CH.sub.2                                                                              164-166                                      2.14  H     CH.sub.3                                                                            ##STR103##                                                  2.15  H     H                                                                                   ##STR104##                                                  2.16  H     CH.sub.3                                                                            ##STR105##     191-193                                      2.17  H     H                                                                                   ##STR106##                                                  2.18  H     CH.sub.3                                                                            ##STR107##     149-151                                      2.19  H     CH.sub.3                                                                            ##STR108##     187-189                                      2.20  H     H                                                                                   ##STR109##                                                  2.21  6-CH.sub.3                                                                          H                                                                                   ##STR110##                                                  2.22  6-CH.sub.3                                                                          CH.sub.3                                                                            ##STR111##                                                  2.23  H     CH.sub.3                                                                            ##STR112##     169-170                                      2.24  H     CH.sub.3                                                                            ##STR113##     183-185                                      2.25  6-CH.sub.3                                                                          CH.sub.3                                                                            ##STR114##                                                  2.26  H     H                                                                                   ##STR115##                                                  2.27  H     CH.sub.3                                                                            ##STR116##     179-182                                      2.28  H     CH.sub.3                                                                            ##STR117##     161-163                                      2.29  H     CH.sub.3                                                                            ##STR118##                                                  2.30  H     H                                                                                   ##STR119##                                                  2.31  H     H                                                                                   ##STR120##                                                  2.32  H     H                                                                                   ##STR121##                                                  2.33  H     CH.sub.3                                                                            ##STR122##                                                  2.34  H     CH.sub.3                                                                            ##STR123##                                                  2.35  H     CH.sub.3                                                                           OCH.sub.3                                                    2.36  H     CH.sub.3                                                                           OC.sub.2 H.sub.5                                                                              126-128                                      2.37  H     H    OC.sub.2 H.sub.5                                             2.38  H     CH.sub.3                                                                           CH.sub.2 CH.sub.3                                                                             178-180                                      2.39  H     CH.sub.3                                                                            ##STR124##     171-173                                      2.40  H     H                                                                                   ##STR125##                                                  2.41  H     CH.sub.3                                                                            ##STR126##     152-154                                      2.42  H     H                                                                                   ##STR127##                                                  2.43  H     H                                                                                   ##STR128##     190-192                                      2.44  H     CH.sub.3                                                                            ##STR129##                                                  2.45  H     CH.sub.3                                                                            ##STR130##     235-237                                      2.46  H     H                                                                                   ##STR131##                                                  2.47  H     CH.sub.3                                                                            ##STR132##                                                  2.48  H     CH.sub.3                                                                           CH.sub.3CCl.sub.2                                            2.49  H     CH.sub.3                                                                            ##STR133##     155-157                                      2.50  H     CH.sub.3                                                                            ##STR134##                                                  2.51  H     CH.sub.3                                                                            ##STR135##     173-176                                      2.52  H     CH.sub.3                                                                            ##STR136##                                                  2.53  H     CH.sub.3                                                                            ##STR137##                                                  2.54  H     H                                                                                   ##STR138##                                                  2.55  H     CH.sub.3                                                                            ##STR139##                                                  2.56  H     CH.sub.3                                                                           (CH.sub.3).sub.2 CHO                                         2.57  H     CH.sub.3                                                                            ##STR140##                                                  2.58  H     CH.sub.3                                                                            ##STR141##                                                  2.59  H     CH.sub.3                                                                            ##STR142##                                                  2.60  H     H                                                                                   ##STR143##                                                  2.61  H     CH.sub.3                                                                            ##STR144##                                                  2.62  H     CH.sub.3                                                                            ##STR145##                                                  2.63  H     CH.sub.3                                                                           CH.sub.2 OCH.sub.3                                                                            161-163                                      __________________________________________________________________________

                  TABLE 3                                                         ______________________________________                                        Compounds of formula I:                                                        ##STR146##                  (I)                                              Comp.                Pos.                                                     No.    R     R.sub.1                                                                              R.sub.2                                                                              SO.sub.2                                                                            A   A m.p. [°C.]                      ______________________________________                                        3.01   H     H      OCH.sub.3                                                                            2     3   OCH.sub.2 CH.sub.2 Cl                    3.02   H     H      CH.sub.3                                                                             2     3   OCHF.sub.2                               3.03   H     H      OCH.sub.3                                                                            2     3   SO.sub.2 CH.sub.2 CH.sub.3               3.04   H     H      OCH.sub.3                                                                            2     3                                                                                  ##STR147##                              ______________________________________                                    

                  TABLE 4                                                         ______________________________________                                        Compounds of formula XIa:                                                      ##STR148##                  (XIa)                                            Comp.                                                                         No.      R       R.sub.4   R.sub.6 m.p. [°C.]                          ______________________________________                                        4.01     H       CH.sub.3  CH.sub.3                                                                              51-52                                      4.02     H       CH.sub.3  phenyl  86-87                                      4.03     H       CH.sub.3  CHCl.sub.2                                                                            105-107                                    4.04     H       CH.sub.3  CH.sub.2 OCH.sub.3                                                                    82-83                                      4.05     H       H         H                                                  4.06     H       H         CH.sub.3                                           4.07     H       CH.sub.3  H       n.sub.D.sup.22 : 1.5582                    4.08     6-CH.sub.3                                                                            CH.sub.3  CH.sub.3                                           ______________________________________                                    

Biological Examples Example B 1: Postemergence phytotoxic action of theherbicides of formula I and of the mixtures of herbicide and safener offormula II on maize

Maize is grown under greenhouse conditions in plastics pots to the 2.5leaf stage. At that stage, a herbicide of formula I alone and also amixture of the herbicide and safeners of formula II are applied to thetest plants. Application is in the form of an aqueous suspension of thetest compounds in 500 1 water/ha. The rates of application for theherbicide are 125/60/30/15/8 and 250/125/60 g/ha, respectively, and therates of application for the safener are 60 g/ha. Evaluation is made 23days after the application using a scale of percentages. 100% indicatesthat the test plant has withered, 0% indicates no phytotoxic action. Theresults show that the safeners used can significantly reduce the damagecaused to maize by the herbicide. Examples of the good protectiveactivity of the safeners are given in Table B1.

                  TABLE B1                                                        ______________________________________                                        Herbicide           Herbicide concentration g/ha                              Comp. No.                                                                              Safener, g/ha                                                                            250     125  60   30  15   8                              ______________________________________                                        3.04     --                 95   90   90  70   65                             3.04     IIb  60             5    0    0   0    0                             3.03     --         90      80   70                                           3.03     IIb  60    50      30   10                                           ______________________________________                                    

Example B2: Use of a mixture of herbicide of formula I and safener offormula II for dressing maize seed

Maize seed is dressed with a safener in an amount corresponding to 1g/kg seed. The maize is then grown under greenhouse conditions inplastics pots to the 2.5 leaf stage. In parallel with the treated maize,untreated maize is cultivated to the same stage. At that stage theherbicide of formula I is applied to treated and untreated test plants.Application is in the form of an aqueous suspension of the herbicide in500 l water/ha. The rate of application for the herbicide is 125, 60,30, 15 and 250/125/60 g/ha, respectively, and the rate of applicationfor the seed-dressing safener of formula II is 1 g/kg seed. Evaluationis made 14 days after the application using a scale of percentages. 100%indicates that the test plant has withered, 0% indicates no phytotoxicaction. The results show that the safener as a seed-dressing agentsignificantly reduces the damage caused by the herbicide postemergence.Similar results are obtained when the herbicide is applied preemergence.Examples of the good activity of the safeners of formula II are shown inTable B2:

                  TABLE B2                                                        ______________________________________                                        Herbicide              Herbicide concentration g/ha                           Comp. No.                                                                              Safener, g/kg seed                                                                          250    125  60   30   15                               ______________________________________                                        3.04                          90   80   50                                    3.04     IIa  1               10   10   10                                    3.02     --                        100  95   95                               3.02     IIa  1                    65   50   25                               3.03     --            90     80   70                                         3.03     IIa  1         0      0    0                                         ______________________________________                                    

Example B3: Postemergence phytotoxic action of the herbicides of formulaI and of the mixtures of herbicide and safener of formula II in sugarcane

Sugar cane is grown under greenhouse conditions in plastics pots to the3-leaf stage. At that stage, a herbicide of formula I alone and also amixture of the herbicide and safeners of formula II are applied to thetest plants. Application is in the form of an aqueous suspension of thetest compounds in 500 l water/ha. The rates of application for theherbicide are 120/60/30 g/ha and the rates of application for thesafener are 60 g/ha.

Evaluation is made 21 days after application using a scale ofpercentages. 100% indicates that the test plant has withered, 0%indicates no phytotoxic action. The results show that the safeners usedcan significantly reduce the damage caused to sugar cane by theherbicide. Examples of the good protective activity of the safeners aregiven in Table B3:

                  TABLE B3                                                        ______________________________________                                        Herbicide              Herbicide concentration g/ha                           Comp. No.   Safener, g/ha                                                                            120       60  30                                       ______________________________________                                        1.01        --         50        30  15                                       1.01        IIb  60    30         0   0                                       1.01        IIc  60    25         5   0                                       ______________________________________                                    

Example B4: Preemergence herbicidal action

Plastics pots are filled with expanded vermiculite. The test compoundsare then applied in such a manner that the final concentration in thenutrient medium is 70 ppm. The seeds of monocotyledonous anddicotyledonous test plants are then sown and cultivated in a climaticchamber under optimum conditions. Evaluation is made 10 days later usinga scale of nine ratings (1=complete destruction, 9=no activity). Ratingsfrom 1 to 4 (especially from 1 to 3) indicate good to very goodherbicidal activity. Examples of the good herbicidal activity of thecompounds of formula Ib are given in Table B4:

                  TABLE B4                                                        ______________________________________                                        Preemergence action of herbicides of formula Ib:                              Concentration of the test compound emulsion: 70 ppm                           Test plant:                                                                   Compound No.                                                                             Nasturtium                                                                              Agrostis Stellaria                                                                             Digitaria                               ______________________________________                                        1.01       2         2        2       2                                       1.02       3         3        3       3                                       1.03       3         3        2       2                                       1.04       3         3        3       3                                       1.31       3         3        3       3                                       1.33       3         3        3       3                                       1.40       3         3        2       2                                       1.45       3         3        3       4                                       1.60       3         3        3       3                                       1.63       3         3        3       2                                       1.69       3         3        3       4                                       1.80       3         3        3       3                                       1.97       3         3        3       3                                       1.98       4         3        3       3                                       1.100      3         3        3       3                                       1.101      3         3        3       2                                       ______________________________________                                    

Formulation Examples for compounds of formula II or mixtures of the samewith a herbicide of formula I (throughout, percentages are by weight)

    ______________________________________                                        1. Emulsifiable concentrates                                                                       a)      b)     c)                                        ______________________________________                                        compound mixture     25%     40%    50%                                       calcium dodecylbenzenesulfonate                                                                     5%      8%     6%                                       castor oil polyethylene glycol                                                                      5%     --     --                                        ether (36 mol of ethylene oxide)                                              tributylphenol polyethylene glycol                                                                 --      12%     4%                                       ether (30 mol of ethylene oxide)                                              cyclohexanone        --      15%    20%                                       xylene mixture       65%     25%    20%                                       ______________________________________                                    

Emulsions of any desired concentration can be produced from suchconcentrates by dilution with water.

    ______________________________________                                        2. Solutions     a)     b)       c)    d)                                     ______________________________________                                        compound mixture 80%    10%      5%    95%                                    ethylene glycol monomethyl                                                                     20%    --       --    --                                     ether                                                                         polyethylene glycol                                                                            --     70%      --    --                                     (mol. wt. 400)                                                                N-methyl-2-pyrrolidone                                                                         --     20%      --    --                                     epoxidised coconut oil                                                                         --     --       1%     5%                                    petroleum fraction (boiling                                                                    --     --       94%   --                                     range 160-190° C.)                                                     ______________________________________                                    

These solutions are suitable for application in the form of micro-drops.

    ______________________________________                                        3. Granules         a)      b)                                                ______________________________________                                        compound mixture    5%      10%                                               kaolin              94%     --                                                highly dispersed silicic acid                                                                     1%      --                                                attapulgite         --      90%                                               ______________________________________                                    

The active ingredient is dissolved in methylene chloride, the solutionis sprayed onto the carrier, and the solvent is subsequently evaporatedoff in vacuo.

    ______________________________________                                        4. Dusts            a)      b)                                                ______________________________________                                        compound mixture    2%      5%                                                highly dispersed silicic acid                                                                     1%      5%                                                talcum              97%     --                                                kaolin              --      90%                                               ______________________________________                                    

Ready-for-use dusts are obtained by intimately mixing the carriers withthe active ingredient.

    ______________________________________                                        5. Wettable powders                                                                              a)        b)     c)                                        ______________________________________                                        compound mixture   25%       50%    75%                                       sodium lignosulfonate                                                                            5%         5%    --                                        sodium laurylsulfate                                                                             3%        --      5%                                       sodium diisobutylnaphthalene-                                                                    --         6%    10%                                       sulfonate                                                                     octylphenol polyethylene                                                                         --         2%    --                                        glycol ether (7-8 mol of                                                      ethylene oxide)                                                               highly dispersed silicic acid                                                                    5%        10%    10%                                       kaolin             62%       27%    --                                        ______________________________________                                    

The active ingredient is thoroughly mixed with the adjuvants and themixture is thoroughly ground in a suitable mill, affording wettablepowders which can be diluted with water to give suspensions of thedesired concentration.

    ______________________________________                                        6. Emulsifiable concentrates                                                  ______________________________________                                        compound mixture      10%                                                     octylphenol polyethylene glycol                                                                      3%                                                     ether (4-5 mol of ethylene oxide)                                             calcium dodecylbenzenesulfonate                                                                      3%                                                     castor oil polyglycol ether                                                                          4%                                                     (35 mol of ethylene oxide)                                                    cyclohexanone         30%                                                     xylene mixture        50%                                                     ______________________________________                                    

Emulsions of any required concentration can be obtained from thisconcentrate by dilution with water.

    ______________________________________                                        7. Dusts           a)     b)                                                  ______________________________________                                        compound mixture    5%     8%                                                 talcum             95%    --                                                  kaolin             --     92%                                                 ______________________________________                                    

Ready-for-use dusts are obtained by mixing the active ingredient withthe carriers and grinding the mixture in a suitable mill.

    ______________________________________                                        8. Extruder granules                                                          ______________________________________                                        compound mixture   10%                                                        sodium lignosulfonate                                                                             2%                                                        carboxymethylcellulose                                                                            1%                                                        kaolin             87%                                                        ______________________________________                                    

The active ingredient is mixed and ground with the adjuvants, and themixture is subsequently moistened with water. The mixture is extrudedand then dried in a stream of air.

    ______________________________________                                        9. Coated granules                                                            ______________________________________                                        compound mixture      3%                                                      polyethylene glycol (mol. wt. 200)                                                                  3%                                                      kaolin                94%                                                     ______________________________________                                    

The finely ground active ingredient is uniformly applied, in a mixer, tothe kaolin moistened with polyethylene glycol. Non-dusty coated granulesare obtained in this manner.

    ______________________________________                                        10. Suspension concentrates                                                   ______________________________________                                        compound mixuture         40%                                                 ethylene glycol           10%                                                 nonylphenol polyethylene glycol                                                                          6%                                                 ether (15 mol of ethylene oxide)                                              sodium lignosulfonate     10%                                                 carboxymethylcellulose     1%                                                 37% aqueous formaldehyde solution                                                                        0.2%                                               silicone oil in the form of a 75%                                                                        0.8%                                               aqueous emulsion                                                              water                     32%                                                 ______________________________________                                    

The finely ground active ingredient is intimately mixed with theadjuvants, giving a suspension concentrate from which suspensions of anydesired concentration can be obtained by dilution with water.

What is claimed is:
 1. A composition for the selective control of weedsin crops of useful plants, which comprises, as active ingredient,together with inert carriers and adjuvants, a mixture comprisinga) aherbicidally effective amount of a pyridylsulfonylurea of formula I##STR149## wherein R is hydrogen, halogen, C₁ -C₄ alkyl, C₁ -C₄ alkoxyor C₁ -C₄ alkylthio, or is C₁ -C₄ alkyl mono- or poly-substituted byhalogen; R₁ is hydrogen or methyl; R₂ is methyl or methoxy; A is --X--R₃or --N--(R₄)R₅ ; R₃ is C₁ -C₆ alkyl, or C₁ -C₆ alkyl that is mono- orpoly-substituted by halogen, C₁ -C₆ alkoxy, C₃ -C₆ alkenyloxy, C₃ -C₆alkynyloxy or by C₃ -C₆ cycloalkyl, which may for its part beinterrupted by oxygen; or is C₃ -C₆ alkenyl, or C₃ -C₆ alkenyl that ismono- or poly-substituted by halogen, C₁ -C₆ alkoxy, C₃ -C₆ alkenyloxyor by C₃ -C₆ alkynyloxy; or is C₄ -C₆ cycloalkyl, or C₄ -C₆ cycloalkylthat is mono- or poly-substituted by halogen or by C₁ -C₆ alkoxy; or isC₃ -C₆ cycloalkyl that is interrupted by oxygen; or is C₃ -C₆ alkynyl; Xis oxygen or S(O)_(n) ; n is 0, 1 or 2; R₄ is hydrogen, C₁ -C₆ alkyl, orC₁ -C₆ alkyl that is mono- or poly-substituted by halogen, C₁ -C₆alkoxy, C₃ -C₆ alkenyloxy, C₃ -C₆ alkynyloxy or by C₁ -C₆ alkylthio; R₅is hydrogen, C₁ -C₆ alkyl, or C₁ -C₆ alkyl that is mono- orpoly-substituted by halogen, C₁ -C₆ alkoxy, C₃ -C₆ alkenyloxy, C₃ -C₆alkynyloxy or by C₁ -C₆ alkylthio, or is C(O)R₆ ; and R₆ is hydrogen, C₁-C₆ alkyl, C₃ -C₆ cycloalkyl or C₂ -C₆ alkynyl; or is C₁ -C₆ alkyl or C₃-C₆ cycloalkyl each substituted by halogen or by C₁ -C₄ alkoxy; or is C₂-C₆ alkenyl, or C₂ -C₆ alkenyl substituted by halogen; or is phenyl,benzyl, naphthyl or OR₁₂, or phenyl, benzyl or naphthyl each substitutedby halogen, C₁ -C₄ alkyl, C₁ -C₄ haloalkyl, C₁ -C₄ alkoxy, C₁ -C₄haloalkoxy, C₃ -C₆ alkenyloxy, C₃ -C₆ alkynyloxy, nitro, cyano, COOR₁₃,NR₁₅ R₁₆, C(O)NR₁₇ R₁₈, X₁ R₂₀, SO₂ NR₂₁ R₂₂ or by X₂ R₂₃ ; R₁₂ is C₁-C₆ alkyl, C₁ -C₆ haloalkyl, oxetan-3-yl, or C₄ -C₆ cycloalkyl, whichmay for its part be substituted by halogen, C₁ -C₄ alkyl or by C₁ -C₄alkoxy; or is phenyl, benzyl or naphthyl, or phenyl, benzyl or naphthyleach substituted by C₁ -C₄ alkyl, C₁ -C₄ haloalkyl, C₁ -C₄ alkoxy, C₁-C₄ haloalkoxy, C₁ -C₄ alkylthio, C₁ -C₄ haloalkylthio, C₁ -C₄alkylsulfonyl, C₁ -C₄ alkylsulfinyl, nitro, cyano, COOR₂₇, NR₂₅ R₂₆,CONR₂₈ R₂₉ or by SO₂ NR₃₀ R₁₄ ; or is C₁ -C₆ alkyl substituted by C₁ -C₄alkoxy, C₃ -C₆ cycloalkyl, cyano, COOR₂₄ or by CONR₃₂ R₃₃ ; or is C₃ -C₆alkenyl, C₃ -C₆ haloalkenyl, C₃ -C₆ alkynyl, C₃ -C₆ haloalkynyl, X₃ R₃₅or X₄ R₃₆ ; R₁₃ is hydrogen, C₁ -C₆ alkyl, C₃ -C₆ alkenyl, C₃ -C₆alkynyl or oxetan-3-yl; R₁₄, R₁₅, R₁₆, R₁₇, R₁₈, R₂₁, R₂₂, R₂₅, R₂₆,R₂₈, R₂₉, R₃₀, R₃₂ and R₃₃ are each independently of the othershydrogen, C₁ -C₄ alkyl, C₃ -C₆ alkenyl or C₃ -C₆ alkynyl; or R₁₅ and R25are each independently of the other the groups --C(O)--X₅ --C₁ -C₄ alkylor --C(O)--C₁ -C₄ alkyl, which may for their part be substituted byhalogen; or R₁₅ and R₁₆ or R₁₇ and R₁₈ or R₂₁ and R₂₂ or R₂₅ and R₂₆ orR₂₈ and R₂₉ or R₃₀ and R₁₄ or R₃₂ and R₃₃ together form a C₄ -C₅alkylene chain, which may for its part be interrupted by oxygen or byNR₁₉, R₁₉ is hydrogen, C₁ -C₄ alkyl, C₃ -C₆ alkenyl or C₃ -C₆ alkynyl;R₂₀ and R₃₅ are each independently of the other C₁ -C₄ alkyl or C₁ -C₄haloalkyl; R₂₃ and R₃₆ are each independently of the other C₁ -C₄ alkylsubstituted by COOR₃₄ ; R₂₄, R₂₇ and R₃₄ are each independently of theother hydrogen or C₁ -C₄ alkyl; X₁ and X₃ are each independently of theother sulfur, SO or SO₂ ; X₂ and X₄ are each independently of the otheroxygen or sulfur; X₅ is oxygen or NR₃₇ ; and R₃₇ is hydrogen, C₁ -C₄alkyl, C₃ -C₆ alkenyl or C₃ -C₆ alkynyl; or an N-oxide or a salt of acompound of formula I, and b) a herbicide-antagonistically effectiveamount of a sulfamoylphenylurea of formula II ##STR150## wherein A₂ is aradical from the group ##STR151## R₇ and R₈ are each independently ofthe other hydrogen, C₁ -C₈ alkyl, C₃ -C₈ cycloalkyl, C₃ -C₆ alkenyl, C₃-C₆ alkynyl or ##STR152## or are C₁ -C₄ alkyl substituted by C₁ -C₄alkoxy or by ##STR153## R₇ and R₈ together form a C₄ -C₆ alkylenebridge, or a C₄ -C₆ alkylene bridge interrupted by oxygen, sulfur, SO,SO₂, NH or by --N(C₁ -C₄ alkyl)--; R₉ is hydrogen or C₁ -C₄ alkyl; R₁₀and R₁₁ are each independently of the other hydrogen, halogen, cyano,nitro, trifluoromethyl, C₁ -C₄ alkyl, C₁ -C₄ alkoxy, C₁ -C₄ alkylthio,C₁ -C₄ alkylsulfinyl, C₁ -C₄ alkylsulfonyl, --COOR_(j), CONR_(k) R_(m),--COR_(n), --SO₂ NR_(k) R_(m) or --OSO₂ --C₁ -C₄ alkyl; or R₁₀ and R₁₁together form a C₃ -C₄ alkylene bridge, which may be substituted byhalogen or by C₁ -C₄ alkyl, or a C₃ -C₄ alkenylene bridge, which may besubstituted by halogen or by C₃ - or C₄ -alkyl, or a butadienylenebridge, which may be substituted by halogen or by C₁ -C₄ alkyl, andR_(g) and R_(h) are each independently of the other hydrogen, halogen,C₁ -C₄ alkyl, trifluoromethyl, methoxy, methylthio or --COOR_(j) ; R_(c)is hydrogen, halogen, C₁ -C₄ alkyl or methoxy; R_(d) is hydrogen,halogen, nitro, C₁ -C₄ alkyl, C₁ -C₄ alkoxy, C₁ -C₄ alkylthio, C₁ -C₄alkylsulfinyl, C₁ -C₄ alkylsulfonyl, --COOR_(j) or --CONR_(k) R_(m) ;and R_(e) is hydrogen, halogen, halo-C₁ -C₄ alkyl, C₁ -C₄ alkyl,--COOR_(j), trifluoromethyl or methoxy; or R_(d) and R_(e) together forma C₃ -C₄ alkylene bridge; R_(f) is hydrogen, halogen or C₁ -C₄ alkyl;R_(x) and R_(y) are each independently of the other hydrogen, halogen,C₁ -C₄ alkyl, C₁ -C₄ alkoxy, C₁ -C₄ alkylthio, --COOR₁₇,trifluoromethyl, nitro or cyano; R₁₇ is hydrogen, C₁ -C₁₀ alkyl, C₁ -C₄alkoxy-C₁ -C₄ alkyl, C₁ -C₄ alkylthio-C₁ -C₄ alkyl, di-C₁ -C₄alkylamino-C₁ -C₄ alkyl, halo-C₁ -C₈ alkyl, C₂ -C₈ alkenyl, halo-C₂ -C₈alkenyl, C₃ -C₈ alkynyl, C₃ -C₇ cycloalkyl, halo-C₃ -C₇ cycloalkyl, C₁-C₈ alkylcarbonyl, allylcarbonyl, C₃ -C₇ cycloalkylcarbonyl, benzoylthat is unsubstituted or mono- to tri-substituted in the phenyl ring bythe same or different substituents selected from halogen, C₁ -C₄ alkyl,halo-C₁ -C₄ alkyl, halo-C₁ -C₄ alkoxy and C₁ -C₄ alkoxy; or is furoyl orthienyl; or is C₁ -C₄ alkyl substituted by phenyl, halophenyl, C₁ -C₄alkylphenyl, C₁ -C₄ alkoxyphenyl, halo-C₁ -C₄ alkylphenyl, halo-C₁ -C₄alkoxyphenyl, C₁ -C₆ alkoxycarbonyl, C₁ -C₄ alkoxy-C₁ -C₈alkoxycarbonyl, C₃ -C₈ alkenyloxycarbonyl, C₃ -C₈ alkynyloxycarbonyl, C₁-C₈ alkylthiocarbonyl, C₃ -C₈ alkenylthiocarbonyl, C₃ -C₈alkynylthiocarbonyl, carbamoyl, mono-C₁ -C₄ alkylaminocarbonyl or bydi-C₁ -C₄ alkylaminocarbonyl; or is phenylaminocarbonyl that isunsubstituted or mono- to tri-substituted in the phenyl ring by the sameor different substituents selected from halogen, C₁ -C₄ alkyl, halo-C₁-C₄ alkyl, halo-C₁ -C₄ alkoxy and C₁ -C₄ alkoxy or that ismono-substituted in the phenyl ring by cyano or by nitro; or isdioxolan-2-yl that is unsubstituted or substituted by one or two C₁ -C₄alkyl radicals; or is dioxan-2-yl that is unsubstituted or substitutedby one or two C₁ -C₄ alkyl radicals; or is C₁ -C₄ alkyl that issubstituted by cyano, nitro, carboxy or by C₁ -C₈ alkylthio-C₁ -C₈alkoxycarbonyl; R_(j), R_(k) and R_(m) are each independently of theothers hydrogen or C₁ -C₄ alkyl; or R_(k) and R_(m) together form a C₄-C₆ alkylene bridge, or a C₄ -C₆ alkylene bridge interrupted by oxygen,NH or by --N(C₁ -C₄ alkyl)--; and R_(n) is C₁ -C₄ alkyl, phenyl, orphenyl substituted by halogen, C₁ -C₄ alkyl, methoxy, nitro or bytrifluoromethyl; or a salt of a compound of formula II.
 2. A compositionaccording to claim 1, wherein R₆ is hydrogen, C₁ -C₆ alkyl or C₃ -C₆cycloalkyl.
 3. A composition according to claim 1, wherein R₃ is C₁ -C₆alkyl, or C₁ -C₆ alkyl that is mono- or poly-substituted by halogen, C₁-C₆ alkoxy, C₃ -C₆ alkenyloxy, C₃ -C₆ alkynyloxy or by C₃ -C₆cycloalkyl, which may for its part be interrupted by oxygen; or is C₃-C₆ alkenyl, or C₃ -C₆ alkenyl that is mono- or poly-substituted byhalogen, C₁ -C₆ alkoxy, C₃ -C₆ alkenyloxy or by C₃ -C₆ alkynyloxy; or isC₄ -C₆ cycloalkyl, or C₄ -C₆ cycloalkyl that is mono- orpoly-substituted by halogen or by C₁ -C₆ alkoxy or may be interrupted byoxygen; or is C₃ -C₆ alkynyl; and R₆ is hydrogen or C₁ -C₆ alkyl.
 4. Acomposition according to claim 1, wherein R₆ is hydrogen, C₁ -C₆ alkyl,C₃ -C₆ cycloalkyl or C₂ -C₆ alkynyl; or is C₁ -C₆ alkyl or C₃ -C₆cycloalkyl each substituted by halogen or by C₁ -C₄ alkoxy; or is C₂ -C₆alkenyl, or C₂ -C₆ alkenyl substituted by halogen.
 5. A compositionaccording to claim 1, wherein, in the compound of formula II, A₂ is aradical of the formula ##STR154## wherein R_(g) and R_(h) are eachindependently of the other hydrogen, halogen, C₁ -C₄ alkyl,trifluoromethyl, methoxy, methylthio or COOR_(j) ; R_(c) is hydrogen,halogen, C₁ -C₄ alkyl or methoxy; R_(d) is hydrogen, halogen, nitro, C₁-C₄ alkyl, C₁ -C₄ alkoxy, C₁ -C₄ alkylthio, C₁ -C₄ alkylsulfinyl, C₁ -C₄alkylsulfonyl, --COOR_(j) or --CONR_(k) R_(m) ; and R_(e) is hydrogen,halogen, C₁ -C₄ alkyl, --COOR_(j), trifluoromethyl or methoxy; or R_(d)and R_(e) together form a C₃ - or C₄ -alkylene bridge; R_(f) ishydrogen, halogen or C₁ -C₄ alkyl; R_(j), R_(k) and R_(m) are eachindependently of the others hydrogen or C₁ -C₄ alkyl; or R_(k) and R_(m)together form a C₄ -C₆ alkylene bridge, or a C₄ -C₆ alkylene bridgeinterrupted by oxygen, NH or by --N(C₁ -C₄ alkyl)--.
 6. A compositionaccording to claim 5, wherein, in the compound of formula II, R_(c),R_(d), R_(e), R_(g) and R_(h) are each independently of the othershydrogen, C₁ -C₄ alkyl or methoxy.
 7. A composition according to claim1, wherein, in the compound of formula II, each of R₁₀ and R₁₁ ishydrogen.
 8. A composition according to claim 1, wherein, in thecompound of formula II, each of R₉, R₁₀ and R₁₁ is hydrogen.
 9. Acomposition according to claim 1, wherein the pyridylsulfonylurea offormula I is a compound of formula Ia ##STR155##
 10. A compositionaccording to claim 9, wherein R is hydrogen.
 11. A composition accordingto claim 10, wherein each of R and R₁ is hydrogen and A is the group##STR156## or --SO₂ --C₁ -C₄ alkyl.
 12. A composition according to claim9, wherein A is --X--R₃.
 13. A composition according to claim 9, whereinA is --N--(R₄)R₅.
 14. A composition according to claim 9, wherein R₅ isC(O)R₆.
 15. A composition according to claim 9, wherein each of R and R₁is hydrogen and A is difluoromethoxy or the group ##STR157##
 16. Acomposition according to claim 9, wherein the sulfamoylphenylurea offormula II is a compound of formula IIf ##STR158## and A₃ is the group##STR159##
 17. A composition according to claim 16, wherein, in thecompound of formula IIf, each of R₈ and R₉ is hydrogen or methyl.
 18. Acomposition according to claim 9, which comprises as compound of formulaII a compound of formula IIa ##STR160## or of formula IIb ##STR161## orof formula IIc ##STR162## or of formula IId ##STR163## or of formula IIe##STR164##
 19. A compound of the formula Ib ##STR165## wherein R ishydrogen, halogen, C₁ -C₄ alkyl, C₁ -C₄ alkoxy or C₁ -C₄ alkylthio, oris C₁ -C₄ alkyl mono- or poly-substituted by halogen; R₁ is hydrogen ormethyl; R₂ is methyl or methoxy; R₄ is hydrogen, C₁ -C₆ alkyl, or C₁ -C₆alkyl that is mono- or poly-substituted by halogen, C₁ -C₆ alkoxy, C₃-C₆ alkenyloxy, C₃ -C₆ alkynyloxy or by C₁ -C₆ alkylthio; R₆ ishydrogen, C₁ -C₆ alkyl, C₃ -C₆ cycloalkyl or C₂ -C₆ alkynyl; or is C₁-C₆ alkyl or C₃ -C₆ cycloalkyl each substituted by halogen or by C₁ -C₄alkoxy; or is C₂ -C₆ alkenyl, or C₂ -C₆ alkenyl substituted by halogen;or is phenyl, benzyl, naphthyl or OR₁₂, or phenyl, benzyl or naphthyleach substituted by halogen, C₁ -C₄ alkyl, C₁ - C₄ haloalkyl, C₁ -C₄alkoxy, C₁ -C₄ haloalkoxy, C₃ -C₆ alkenyloxy, C₃ -C₆ alkynyloxy, nitro,cyano, COOR₁₃, NR₁₅ R₁₆, C(O)NR₁₇ R₁₈, X₁ R₂₀, SO₂ NR₂₁ R₂₂ or by X₂ R₂₃; R₁₂ is C₁ -C₆ alkyl, C₁ -C₆ haloalkyl, oxetan-3-yl, or C₄ -C₆cycloalkyl, which may for its part be substituted by halogen, C₁ -C₄alkyl or by C₁ -C₄ alkoxy; or is phenyl, benzyl or naphthyl, or phenyl,benzyl or naphthyl each substituted by C₁ -C₄ alkyl, C₁ -C₄ haloalkyl,C₁ -C₄ alkoxy, C₁ -C₄ haloalkoxy, C₁ -C₄ alkylthio, C₁ -C₄haloalkylthio, C₁ -C₄ alkylsulfonyl, C₁ -C₄ alkylsulfinyl, nitro, cyano,COOR₂₇, NR₂₅ R₂₆, CONR₂₈ R₂₉ or by SO₂ NR₃₀ R₁₄ ; or is C₁ -C₆ alkylsubstituted by C₁ -C₄ alkoxy, C₃ -C₆ cycloalkyl, cyano, COOR₂₄ or byCONR₃₂ R₃₃ ; or is C₃ -C₆ alkenyl, C₃ -C₆ haloalkenyl, C₃ -C₆ alkynyl,C₃ -C₆ haloalkynyl, X₃ R₃₅ or X₄ R₃₆ ; R₁₃ is hydrogen, C₁ -C₆ alkyl, C₃-C₆ alkenyl, C₃ -C₆ alkynyl or oxetan-3-yl; R₁₄, R₁₅, R₁₆, R₁₇, R₁₈,R₂₁, R₂₂, R₂₅, R₂₆, R₂₈, R₂₉, R₃₀, R₃₂ and R₃₃ are each independently ofthe others hydrogen, C₁ -C₄ alkyl, C₃ -C₆ alkenyl or C₃ -C₆ alkynyl; orR₁₅ and R₂₅ are each independently of the other the groups --C(O)--X₅--C₁ -C₄ alkyl or --C(O)--C₁ -C₄ alkyl, which may for their part besubstituted by halogen; or R₁₅ and R₁₆ or R₁₇ and R₁₈ or R₂₁ and R₂₂ orR₂₅ and R₂₆ or R₂₈ and R₂₉ or R₃₀ and R₁₄ or R₃₂ and R₃₃ together form aC₄ -C₅ alkylene chain, which may for its part be interrupted by oxygenor by NR₁₉, R₁₉ is hydrogen, C₁ -C₄ alkyl, C₃ -C₆ alkenyl or C₃ -C₆alkynyl; R₂₀ and R₃₅ are each independently of the other C₁ -C₄ alkyl orC₁ -C₄ haloalkyl; R₂₃ and R₃₆ are each independently of the other C₁ -C₄alkyl substituted by COOR34; R₂₄, R₂₇ and R₃₄ are each independently ofthe other hydrogen or C₁ -C₄ alkyl; X₁ and X₃ are each independently ofthe other sulfur, SO or SO₂ ; X₂ and X₄ are each independently of theother oxygen or sulfur; X₅ is oxygen or NR₃₇ ; and R₃₇ is hydrogen, C₁-C₄ alkyl, C₃ -C₆ alkenyl or C₃ -C₆ alkynyl.
 20. A compound according toclaim 19, wherein R₆ is hydrogen or C₁ -C₆ alkyl.
 21. A method ofselectively controlling weeds and grasses in crops of useful plants,which comprises treating the crops, their seed or the crop area thereofwith an effective amount of a pyridylsulfonylurea herbicide of formula I##STR166## or an N-oxide or a salt thereof, and aherbicide-antagonistically effective amount of a sulfamoylphenylureacompound of formula II ##STR167## or a salt thereof, simultaneously orindependently of one another, wherein R is hydrogen, halogen, C₁ -C₄alkyl, C₁ -C₄ alkoxy or C₁ -C₄ alkylthio, or is C₁ -C₄ alkyl mono- orpoly-substituted by halogen; R₁ is hydrogen or methyl; R₂ is methyl ormethoxy; A is --X--R₃ or --N--(R₄)R₅ ; R₃ is C₁ -C₆ alkyl, or C₁ -C₆alkyl that is mono- or poly-substituted by halogen, C₁ -C₆ alkoxy, C₃-C₆ -alkenyloxy C₃ -C₆ alkynyloxy or by C₃ -C₆ cycloalkyl, which may forits part be interrupted by oxygen; or is C₃ -C₆ alkenyl, or C₃ -C₆alkenyl that is mono- or poly-substituted by halogen, C₁ -C₆ alkoxy, C₃-C₆ alkenyloxy or by C₃ -C₆ alkynyloxy; or is C₄ -C₆ cycloalkyl, or C₄-C₆ cycloalkyl that is mono- or poly-substituted by halogen or by C₁ -C₆alkoxy; or is C₃ -C₆ cycloalkyl that is interrupted by oxygen; or is C₃-C₆ alkynyl; X is oxygen or S(O)_(n) ; n is0, 1 or2; R₄ is hydrogen, C₁-C₆ alkyl, or C₁ -C₆ alkyl that is mono- or poly-substituted by halogen,C₁ -C₆ alkoxy, C₃ -C₆ alkenyloxy, C₃ -C₆ alkynyloxy or by C₁ -C₆alkylthio; R₅ is hydrogen, C₁ -C₆ alkyl, or C₁ -C₆ alkyl that is mono-or poly-substituted by halogen, C₁ -C₆ alkoxy, C₃ -C₆ alkenyloxy, C₃ -C₆alkynyloxy or by C₁ -C₆ alkylthio, or is C(O)R₆ ; and R₆ is hydrogen, C₁-C₆ alkyl, C₃ -C₆ cycloalkyl or C₂ -C₆ alkynyl; or is C₁ -C₆ alkyl or C₃-C₆ cycloalkyl each substituted by halogen or by C₁ -C₄ alkoxy; or is C₂-C₆ alkenyl, or C₂ -C₆ alkenyl substituted by halogen; or is phenyl,benzyl, naphthyl or OR₁₂, or phenyl, benzyl or naphthyl each substitutedby halogen, C₁ -C₄ alkyl, C₁ -C₄ haloalkyl, C₁ -C₄ alkoxy, C₁ -C₄haloalkoxy, C₃ -C₆ alkenyloxy, C₃ -C₆ alkynyloxy, nitro, cyano, COOR₁₃,NR₁₅ R₁₆, C(O)NR₁₇ R₁₈, X₁ R₂₀, SO₂ NR₂₁ R₂₂ or by X₂ R₂₃ ; R₁₂ is C₁-C₆ alkyl, C₁ -C₆ haloalkyl, oxetan-3-yl, or C₄ -C₆ cycloalkyl, whichmay for its part be substituted by halogen, C₁ -C₄ alkyl or by C₁ -C₄alkoxy; or is phenyl, benzyl or naphthyl, or phenyl, benzyl or naphthyleach substituted by C₁ -C₄ alkyl, C₁ -C₆ haloalkyl, C₁ -C₄ alkoxy, C₁-C₄ haloalkoxy, C₁ -C₄ C₁ -C₄ haloalkylthio, C₁ -C₄ alkylsulfonyl, C₁-C₄ alkylsulfinyl, nitro, cyano, COOR₂₇, NR₂₅ R₂₆, CONR₂₈ R₂₉ or by SO₂NR₃₀ R₁₄ ; or is C₁ -C₆ alkyl substituted by C₁ -C₄ alkoxy, C₃ -C₆-cycloalkyl cyano, COOR₂₄ or by CONR₃₂ R₃₃ ; or is C₃ -C₆ alkenyl, C₃-C₆ haloalkenyl, C₃ -C₆ alkynyl, C₃ -C₆ haloalkynyl, X₃ R₃₅ or X₄ R₃₆ ;R₁₃ is hydrogen, C₁ -C₆ alkyl, C₃ -C₆ alkenyl, C₃ -C₆ alkynyl oroxetan-3-yl; R₁₄, R₁₅, R₁₆, R₁₇, R₁₈, R₂₁, R₂₂, R₂₅, R₂₆, R₂₈, R₂₉, R₃₀,R₃₂ and R₃₃ are each independently of the others hydrogen, C₁ -C₄ alkyl,C₃ -C₆ alkenyl or C₃ -C₆ alkynyl; or R₁₅ and R₂₅ are each independentlyof the other the groups --C(O)--X₅ --C₁ -C₄ alkyl or --C(O)--C₁ -C₄alkyl, which may for their part be substituted by halogen; or R₁₅ andR₁₆ or R₁₇ and R₁₈ or R₂₁ and R₂₂ or R₂₅ and R₂₆ or R₂₈ and R₂₉ or R₃₀and R₁₄ or R₃₂ and R₃₃ together form a C₄ -C₈ alkylene chain, which mayfor its part be interrupted by oxygen or by NR₁₉, R₁₉ is hydrogen, C₁-C₄ alkyl, C₃ -C₆ alkenyl or C₃ -C₆ alkynyl; R₂₀ and R₃₅ are eachindependently of the other C₁ -C₆ alkyl or C₁ -C₄ haloalkyl; R₂₃ and R₃₆are each independently of the other C₁ -C₄ alkyl substituted by COOR₃₄ ;R₂₄, R₂₇ and R₃₄ are each independently of the other hydrogen or C₁ -C₄alkyl; X₁ and X₃ are each independently of the other sulfur, SO or SO₂ ;X₂ and X₄ are each independently of the other oxygen or sulfur; X₅ isoxygen or NR₃₇ ; R₃₇ is hydrogen, C₁ -C₄ alkyl, C₃ -C₆ alkenyl or C₃ -C₆alkynyl; A₂ is a radical from the group ##STR168## R₇ and R₈ are eachindependently of the other hydrogen, C₁ -C₈ alkyl, C₃ -C₈ cycloalkyl, C₃-C₆ alkenyl, C₃ -C₆ alkynyl or ##STR169## or are C₁ -C₄ alkylsubstituted by C₁ -C₄ alkoxy or by ##STR170## R₇ and R₈ together form aC₄ -C₆ alkylene bridge, or a C₄ -C₆ alkylene bridge interrupted byoxygen, sulfur, SO, SO₂, NH or by --N(C₁ -C₄ alkyl)--; R₉ is hydrogen orC₁ -C₄ alkyl; R₁₀ and R₁₁ are each independently of the other hydrogen,halogen, cyano, nitro, trifluoromethyl, C₁ -C₄ alkyl, C₁ -C₄ alkoxy, C₁-C₄ alkylthio, C₁ -C₄ alkylsulfinyl, C₁ -C₄ alkylsulfonyl, --COOR_(j),CONR_(k) R_(m), --COR_(n), --SO₂ NR_(k) R_(m) or --OSO₂ -C₁ -C₄ alkyl;or R₁₀ and R₁₁ together form a C₃ -C₄ alkylene bridge, which may besubstituted by halogen or by C₁ -C₄ alkyl, or a C₃ -C₄ alkenylenebridge, which may be substituted by halogen or by C₃ - or C₄ -alkyl, ora butadienylene bridge, which may be substituted by halogen or by C₁ -C₄alkyl, and R_(g) and R_(h) are each independently of the other hydrogen,halogen, C₁ -C₄ alkyl, trifluoromethyl, methoxy, methylthio or--COOR_(j) ; R_(c) is hydrogen, halogen, C₁ -C₄ alkyl or methoxy; R_(d)is hydrogen, halogen, nitro, C₁ -C₄ alkyl, C₁ -C₄ alkoxy, C₁ -C₄alkylthio, C₁ -C₄ alkylsulfinyl, C₁ -C₄ alkylsulfonyl, --COOR_(j) or--CONR_(k) R_(m) ; and R_(e) is hydrogen, halogen, halo-C₁ -C₄ alkyl, C₁-C₄ alkyl, --COOR_(j), trifluoromethyl or methoxy; or R_(d) and R_(e)together form a C₃ -C₄ alkylene bridge; R_(f) is hydrogen, halogen or C₁-C₄ alkyl; R_(x) and R_(y) are each independently of the other hydrogen,halogen, C₁ -C₄ alkyl, C₁ -C₄ alkoxy, C₁ -C₄ alkylthio, --COOR₁₇,trifluoromethyl, nitro or cyano; R₁₇ is hydrogen, C₁ -C₁₀ alkyl, C₁ -C₄alkoxy-C₁ -C₄ alkyl, C₁ -C₄ alkylthio-C₁ -C₄ alkyl, di-C₁ -C₄alkylamino-C₁ -C₄ alkyl, halo-C₁ -C₈ alkyl, C₂ -C₈ alkenyl, halo-C₂ -C₈alkenyl, C₃ -C₈ alkynyl, C₃ -C₇ cycloalkyl, halo-C₃ -C₇ cycloalkyl, C₁-C₈ alkylcarbonyl, allylcarbonyl, C₃ -C₇ cycloalkylcarbonyl, benzoylthat is unsubstituted or mono- to tri-substituted in the phenyl ring bythe same or different substituents selected from halogen, C₁ -C₄ alkyl,halo-C₁ -C₄ alkyl, halo-C₁ -C₄ alkoxy and C₁ -C₄ alkoxy; or is furoyl orthienyl; or is C₁ -C₄ alkyl substituted by phenyl, halophenyl, C₁ -C₄alkylphenyl, C₁ -C₄ -alkoxyphenyl, halo-C₁ -C₄ alkylphenyl, halo-C₁ -C₄alkoxyphenyl, C₁ -C₆ alkoxycarbonyl, C₁ -C₄ alkoxy-C₁ -C₈alkoxycarbonyl, C₃ -C₈ alkenyloxycarbonyl, C₃ -C₈ alkynyloxycarbonyl, C₁-C₈ alkylthiocarbonyl, C₃ -C₈ alkenylthiocarbonyl, C₃ -C₈alkynylthiocarbonyl, carbamoyl, mono-C₁ -C₄ alkylaminocarbonyl or bydi-C₁ -C₄ alkylaminocarbonyl; or is phenylaminocarbonyl that isunsubstituted or mono- to tri-substituted in the phenyl ring by the sameor different substituents selected from halogen, C₁ -C₄ alkyl, halo-C₁-C₄ alkyl, halo-C₁ -C₄ alkoxy and C₁ -C₄ alkoxy or that ismono-substitute in the phenyl ring by cyano or by nitro; or isdioxolan-2-yl that is unsubstituted or substituted by one or two C₁ -C₄alkyl radicals; or is dioxan-2-yl that is unsubstituted or substitutedby one or two C₁ -C₄ alkyl radicals; or is C₁ -C₄ alkyl that issubstituted by cyano, nitro, carboxy or by C₁ -C₈ alkylthio-C₁ -C₈alkoxycarbonyl; R_(j), R_(k) and R_(m) are each independently of theothers hydrogen or C₁ -C₄ alkyl; or R_(k) and R_(m) together form a C₄-C₆ alkylene bridge, or a C₄ -C₆ alkylene bridge interrupted by oxygen,NH or by --N(C₁ -C₄ alkyl)--; and R_(n) is C₁ -C₄ alkyl, phenyl, orphenyl substituted by halogen, C₁ -C₄ alkyl, methoxy, nitro or bytrifluoromethyl.
 22. A method according to claim 21, wherein the cropsor the crop area is treated with from 0.001 to 2 kg/ha of thepyridylsulfonylurea herbicide of formula I or the N-oxide or saltthereof and from 0.005 to 0.5 kg/ha of the sulfamoylphenylurea compoundof formula II or the salt thereof.
 23. A method according to claim 21wherein the crops of useful plants are maize or sugar cane.